Mascara Composition And Method

ABSTRACT

Cationically-charged particulates and compositions containing the cationically-charged particulates for application to keratinous materials are provided. Methods of preparing the cationically-charged particulates are also disclosed. Methods of increasing the cationic charge on particulates are also provided.

FIELD OF THE INVENTION

The invention relates to novel cosmetic compositions suitable forapplication to keratinous materials, such as eyelashes, eyebrows andhair, and to methods of making the compositions. More specifically, theinvention relates to fibers or other particulates which have beenuniformly coated with a cationically-charged material, and tocompositions containing the coated particulates.

BACKGROUND OF THE INVENTION

Consumers desiring longer and thicker eyelashes have traditionallyresorted to the use of false eyelashes which are applied with glue tonatural eyelashes or to costly lash extensions. As an alternative,various mascara products have been popular. Nevertheless, some eyelashesare just too sparse for just any type of volumizing mascara to make themlook more dramatic. On the other hand, even women with a great eyelashfringe may desire a more intense result than may be achieved using theirfavorite mascara. Features that mascara products are expected to haveinclude the ability to darken, thicken and lengthen the eyelashes so asto achieve eyelashes having a fuller appearance without clumping orflaking off. In addition, it is desirable that the product be water-and/or smudge-resistant yet not be difficult to remove. The cosmeticindustry has responded to this demand by providing mascara compositionscontaining fibers, waxes, and/or bulking or filler agents; however,there are limitations on the amount of such ingredients which can beadded to the formulations without reducing processibility of theformula, or interfering both with loading a brush with product anddelivering product from the brush to the eyelashes. Also commerciallyavailable are fibers for application to mascara-coated eyelashes. Adisadvantage associated with such fibers is that when drawn out of areceptacle, the fibers tend to pick up negative charges from theatmosphere which causes them to become statically-charged and to repelone another and fly about. To deal with this issue, fibers have alsobeen formulated into gel products. Nevertheless, fibers in such productsoften do not sufficiently adhere to the eyelashes upon application oreven after dry down but tend to flake off onto the face and into theeyes causing irritation.

There continues to be a need to formulate a fiber-containing compositionwhich will better adhere to the eyelashes, eyebrows or hair to achievethe desired improvements in volume and/or length, and without theaforementioned disadvantages associated with conventional products.

SUMMARY OF THE INVENTION

Embodiments herein relate to cationically-charged particulates, and tocompositions comprising the cationically-charged particulates, forapplication to negatively charged keratinous materials, such aseyelashes, eyebrows and hair. The particulates are provided with thecationic charge by encapsulation with a coating comprising acationically-charged material. The cationically-charged particulates areoptionally coated with a film-former finish material to further seal thecationically-charged coating to the particulates and to render theparticulates hydrophobic. The film-former material may be hydrophilic orhydrophobic, but is hydrophobic on dry-down.

Embodiments herein also relate to methods of preparing thecationically-charged particulates and particulate-containing cosmeticcompositions.

Embodiments herein further provide methods of increasing the cationiccharge of particulates. The methods include coating a rod withcationically charged particulates, contacting the rod with a surface atleast once to generate a static charge, and transferring the staticcharge to the cationically charged particulates on contact.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a sheet of paper onto which statically-charged fibershave scattered from a brush withdrawn from a vial of the virgin fibers.

FIG. 2 depicts a blank sheet of paper onto which film-former coated,cationically-charged fibers have not been released from a brushwithdrawn from a vial of the charged fibers.

FIG. 3 is a photograph showing the scattering of statically-chargedfibers under the right eye after the in the range of from about 0.1 mVto about 400 mV fibers were applied to mascara-coated eyelashes, andfurther showing no scattering of film-former coated,cationically-charged fibers under the left eye after the film-formercoated, cationically-charged fibers were applied to mascara-coatedeyelashes.

FIG. 4 is a photograph of the right eye area taken one hour after theinitial application of statically-charged fibers to mascara-coatedeyelashes followed by wiping the undereye are clean of fallen fibers.

FIG. 5 is a photograph of the left eye area taken one hour after theinitial application of film-former coated, cationically-charged fibersto mascara-coated eyelashes followed by wiping the undereye area clean.

FIG. 6 is a graph showing the amount of treated fibers deposited onlashes (observed visually) as a function of charge of the treatedfibers.

DETAILED DESCRIPTION OF THE INVENTION

The use of coatings on the surfaces of particles has been known for morethan forty years in the personal care industry. Such coatings are widelyused to encapsulate tablets so that they are completely and evenlycoated with a coating material. The benefits of a coated tablet includethe ability, upon degradation of the coating, to absorb materials froman environment; or to release materials, such as active agents disposedin a matrix of the coating, into an environment. As coatings may possessporosity, as in the case of a zeolite, such coating do not requirerelease in order to render absorption or release of a material into orout of the matrix of the coating. In cases such as these, very highselectivity may be obtained by using properly tuned porecharacteristics.

The surface treatment of pigments has also been used to improve theability of incorporating them into cosmetic formulations. For example,pigments coated with different types of silicones are commerciallyavailable and when used as cosmetic pigments in formulations the coatingfacilitates the incorporation of the pigment into hydrophobicformulations whereas the untreated pigment would generally remain poorlydispersed. Other pigments may be coated with fluorocarbon polymers toimprove their adhesive power while also forming a film upon application.Still other pigments may coated with natural polymers such as proteins,for example collagen. These types of coatings do not demonstrate awaterproofing property but the natural proteins do enhance ease ofpigment dispersion into the hydrophilic phase of the cosmeticformulation and may be used to introduce a cationic charges into theformulations. Although protein-coated pigment introduced into thehydrophilic phase demonstrates better binding on dry down, such coatedpigments have not been shown to adhere sufficiently to skin.Additionally, dispersed proteins tends to separate out from suchformulations during manufacturing.

A commonly used material for an encapsulation coating is siliconepolymer. There have been many efforts to improve the adhesion ofparticulates to keratinous materials by coating the particulates withsilicones. Silicone polymers have been widely used because they possesstwo advantageous properties: biocompatibility and permeability to gasesand small molecules. Advantages for use in cosmetics include theircontribution to waterproofing or water-resistance property, feel, andshine, and they also are compatible with most oil phases of a baseformulation. Nevertheless, the use of silicones for coating particulateshas its drawbacks, including excessive shine and incompatibility withwater and water-soluble ingredients.

Nevertheless, prior to the present invention, it had not been known tocoat particulates with a cationically-charged material for formulationinto cosmetic compositions for application to keratinous materials. Dry,treated particulates of the invention demonstrate greater adhesion tonegatively-charged eyelashes, eyebrows and hair compared with untreatedparticulates. The dry, treated particulates may also be incorporatedinto volumizing mascara, eyebrow filler and hair filler formulations toprovide such formulations with superior adhesion to negatively chargedeyelashes, eyebrows and hair.

Keratinous materials have an anionic charge of about −24 mV. The surfaceof particulates, for example, fibers, treated according to the presentinvention, will typically have a net cationic charge in the range offrom about 0.1 mV to about 400 mV which will facilitate their adherenceto the keratinous materials. A net cationic charge of greater than about400 mV would be expected to create dramatic flyaway of the fibers (dueto repellent forces between fibers) when pulling a brush loaded withdry, treated particulates out of a container holding the dry treatedparticulates. When incorporated into a base formulation, treatedparticulates having a net cationic charge of greater than about 400 mVwould tend to be tacky and agglomerate in the container. Particulateswith a net cationic charge of less than about 0.1 mV would not beexpected to adhere sufficiently to eyelashes, eyebrows and/or hair,whether the particulates are used dry or incorporated into a baseformulation.

In accordance with compositions and methods of the present invention,the dry, treated particulates have a net cationic charge, measured asthe zeta potential, in the range of from about 0.1 mV to about 400 mV,such as from about 24 mV to about 200 mV, for example, in the range offrom about 60 mV to about 150 mV.

The cationic charge is imparted to the particulates by means of at leastone coating containing a cationically-charged material. In someembodiments of the present invention, the coating comprises a natural orsynthetic cationic compound dispersed in an aqueous-based medium,preferably a water and alcohol medium, to facilitate evaporation of themedium and drying of the particulates. One class of such compoundsincludes cationically charge-modified polymers where the cationic groupsenhance the polymer's substantivity to anionic substrates, such askeratinous materials. Natural cationically charge-modified polymers maybe derived from various animal and plant sources including guar gum,cellulose, proteins, polypeptides, chitosan, lanolin, and starches andcombinations thereof. Synthetic compounds include those with quaternaryammonium functional groups, for example, cationic polymers, such aspolyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-10,polyquaternium-39, polyquaternium-44, polyquaternium-46, quaternaryammonium salts, including, distearyldimonium chloride,cinnamidopropyltrimonium chloride, cetrimonium chloride, and guarhydroxypropyltrimonium chloride, and combinations of any two or morecationically-charged materials. A cationic coating comprisingpolyquaternium-6 is particularly preferred for its charge density. Afurther example of a cationically-charged coating useful in the presentinvention is powdered iron (FeO).

Particulates coated with the cationically-charged coating mayoptionally, but not necessarily, be further encapsulated with afilm-former finish. The film former aids in the adhesion of thecationically-charged material to the particulate surfaces, andadditionally can be configured to impart hydrophobicity to theparticulate surfaces. So as not to hinder the film former from bindingto the cationically-charged surfaces of the particulates, thecationically-charged coating typically comprises water in an amount ofbetween about 0.01 and 5.00 percent by weight after drying which limitstheir charge density.

The film former coating preferably comprises at least one water-solubleor water-dispersible polymer having a surface tension of less than about75γ, and preferably in the range of from about 20γ to about 65γ. Thepolymers preferably exhibit good water-resistance, adhesion andflexibility on dry down. Film forming polymers useful for encapsulatingthe cationically coated particulates, may be hydrophilic or hydrophobic,but are hydrophobic when dry. Examples of suitable polymers, include,but are not limited to, silicones, such as methyltrimethicone,trimethylsiloxysilicate, and dimethicone, dimethicone andtrimethylsiloxysilicate, and the like; acrylates polymers andcopolymers, such as Syntran PC 5775, Syntran PC 5776, Avalure AC-120,Daitosol 5000AD, Daitosol 5000SJ; Daitosol U9-40, Vinylsol 214oLVinylsol 1086 WP; polyvinylpyrrolidone (PVP) derivatives, such as PVPK-30, PVP/VA E-635, PVP/VA W-735; polyurethanes, such as Luviset P.U.R.,Giovarez P-0580, and Baycusan C 1004; polyvinyl amines and polyvinylacetates. Non-polymeric film-former finishes may include, but are notlimited to, esters, such as sucrose acetate isobutyrate, which may beused alone, or in combination with any of the aforementioned polymers.

In one preferred embodiment of the invention, the film-former coating isa silicone polymer blend. A film former solution may contain, forexample, dimethicone and trimethylsiloxysiliate in trisiloxane. Whendried, this coating creates a high contact angle with the particulateswhich renders the treated particulates particularly compatible withwater-in-oil and water-in-silicone systems. In another preferredmbodiment, a film-former solution contains dimethicone,trimethylsiloxysilicate and polyglyceryl-3 disiloxane dimethicone intrisiloxane. When dried, this film former creates a lesser contactangles with particulates. It possesses hydrophilic (i.e., polyglycerin)side chains which enhance the compatibility of the treated particulatesin oil-in-water and silicone-in-water systems.

The amount of film former used should be an amount sufficient toencapsulate the cationically charged particulates and render themhydrophobic, but not be so great as to decrease the net cationic chargeof the particulates to a level which would reduce the level of cationiccharge below a value useful in the present invention. In the case wherethe treated fibers or a formulation containing the treated fibers, areused on the eyelashes, it is preferred that the cationically-chargedfibers be encapsulated in film former, since oil in the skin around theeyes may dissolve the cationic material on the fibers. The dissolvedcationic material may make contact with and irritate the eyes. The filmformer encapsulation is not necessary where the fibers or a formulationcontaining the fibers will be used on the eyebrows or in the hair.

Additional coatings may be deposited on the particulates prior to thefinal film former finish. Such additional coatings may be liquid orsolid, and may deposit anionic material, cationic material, or both. Insome embodiments of the invention, the additional coatings containproteins, peptides, or a combination thereof. An intervening anioniccoating may be used to balance a high cationic charge of particulatescoated with the initial cationically charged coating. The net cationiccharge may also be modified with the film former coating. A thicker thefilm former coating may also be used to reduce a high cationic charge.The coated particulates, however, carry a net final charge of from about0.1 to about 400 mV so as to adhere satisfactorily to negatively chargedkeratinous materials. One example of a natural intervening coating is anaqueous-containing solution containing 0.1 wt. % grape seed extract. Thecoating, when dried, carries a cationic charge.

Any of the coating compositions may contain compatible actives, such asconditioning and/or rejuvenating ingredients. Benefits of conditioningingredients include added shine, but also flexibility and moisturewhich, for example, when included in mascara, help keep eyelashes,pliable and less likely to dry out and break. Conditioning ingredientsin mascara contribute to a more even mascara application, since wheneyelashes are conditioned, the surfaces are smoother. The smoothersurfaces help pigment in mascara to adhere more evenly to eyelashes.Some of these conditioning agents may be moisturizers which penetratehairs along the lashline, making them softer. Other agents, such ashumectants, may attract moisture into the eyelashes. Still other agents,for example, proteins or peptides, are said to make the eyelashesstronger by reinforcing fibers that make up the hair strands.Additionally, these proteins and/or peptides may help to plump theeyelashes which is particularly beneficial to those with thin or sparseeyelashes.

Examples of conditioning and/or rejuvenating agents useful in theparticulate coatings to promote the health of the eyelashes, mayinclude, but are not limited to, oils, such as argan oil, tea tree oil,jojoba seed oil, avocado oil, and sesame seed oil; humectants,moisturizers and/or lubricants, such as dimethicone, sorbitol, glycerin,polyisobutene, honey derivatives, and sodium hylauronate; Vitamin B₅derivatives, such as panthenol, dexapanthanol, pantethine, lauroyllysine, hydrolyzed keratin, and hydrolyzed wheat protein.

In addition to pigment, e.g. iron oxides, which may be contained in orassociated with, untreated particulates, pigment also may be trapped inany of the coatings, that is, the initial cationic coating, the filmformer finish, or any intervening coatings, to intensify color andpromote volume.

In accordance with the compositions and methods of the presentinvention, particulates, such as fibers or powders, suitable fortreatment according to the present invention, may be made of variousmaterials, naturally-derived, semi-synthetic and/or synthetic. Asnaturally-derived particulates, mention may be made of, for example,cellulose, and cellulose-based materials, including, but not limited to,cellulose (and) magnesium stearate, cotton, linen, and so forth. Alsouseful is polylactic acid, a thermoplastic aliphatic polyester derivedfrom corn starch, tapioca or sugar cane. Also suitable as particulatematter for use in the present invention would be a semi-syntheticmaterial such as rayon, a manufactured and regenerated cellulose fiber.Synthetic particles may include, but are not limited to, those made fromnylon or polypropylene. Synthetic particulates are said to beparticularly useful for imparting volume and length to mascara andeyebrow- and hair-filler products. Synthetic particulates may containpigments such as carbon black or iron oxides to enhance the overallcolor effect of products in which they are incorporated.

Fibers useful in carrying out the invention may have a length in therange of from about 1 micrometer to about 4 millimeters and a weight inthe range of from about 3 to about 20 denier. Preferably, the fibers arefrom about 1 millimeter to about 4 millimeters in length, and have adenier in the range of from about 3 to about 15. In certain preferredembodiments of the invention, the fibers have a length in the range offrom about 1 millimeter to about 2 millimeters, and a denier in therange of from about 5 to about 10. The fibers may take anycross-sectional form, such as round, oval, triangular, hexagonal,heart-shaped, star-shaped, and so forth.

One particularly preferred synthetic fiber is composed of nylon-6 (And)iron oxides (And) triethoxycaprylylsilane (And) silica, and is availableas NFBL-10D-1R-1MM from Kobo Products, Inc. These fibers are black, havea round cross-section, a length of about 1 millimeter and a denier ofabout 10. Another preferred synthetic fiber is SPLASH Fiber II 7T-1MMfrom Kobo Products, Inc. which is composed of nylon-6 (And) silica (And)iron oxides. These fibers have a 7 decitex width (about 6.3 denier), a 1millimeter length, are charcoal black in color, and have a hexagonalcross-section resulting in a “flower” cross-sectional shape. The greatersurface area of these fibers, due to their shape, is also said to offera more volumizing effect to eyelashes to which the mascara is appliedthan would typical fibers having a round to oval cross-section,particularly by filling inbetween sparse lashes. Also useful is FDAcertified carbon black, 10 denier, 1 mm round nylon fiber (nylon-6NFCB-10D-1R-1 mm, available from Daito Kasei Kogyo Co. Ltd.).

In accordance with some embodiments of the invention, the particulatesare in the form of a fine powder which may take the form of aflake-shaped or plate-like, cellulose product, the flakes having athickness of about 1 to 2 micrometers and a width of about 8.8micrometers. Such a powder is available as silk cotton PW fibers, fromKobo Products, Inc.

In some embodiments of the present invention, fibers having variouscross-sectional shapes, lengths and deniers may be blended, with orwithout powders particulates, in compositions of the present inventionto achieve customized formulations for a desired effect; that is,enhanced volume and/or length, when applied to keratinous materials.

In accordance with the present invention, a method of coating particlescomprises encapsulating the particles with at least one cationicallycharged material, for example a cationic polymer, optionally followed bycoating with a water-soluble polymeric film finish coating to furtherseal the cationically charged coating to the particle surfaces. In someembodiments of the invention, the particulates are coated with one ormore additional coats of cationic or anionic material or a combinationthereof, the net cationic charge of the final dried particulates fallingwithin a range of from about 0.1 mV to about 400 mV. One skilled in theart would appreciate that any method which will coat the particulatesmay be used as long as the treated particulates retain a net catoniccharge in the range of from about 0.1 mV to about 400 mV.

One known method of coating or encapsulating particles, for example,fibers, is spray coating. Fibers are introduced into a reactor ormicrofluidizer which acts like a vortex. Air is pumped into a chamber ofthe fluidizer from the bottom cauising the fibers to fly around. Thevolume of air flow (i.e., flap) is controlled to prevent the lightweight fibers from clogging the fluidizer filter. Thereafter, asolution, a dispersion, or an aqueous-containing emulsion, of a sprayformulation containing a cationically charged material is introducedinto the microfluidizer, and the circulating fibers are coated with thecationically-charged solution. The spray composition is sprayed by oneor more nozzles situated in various regions of the microfluidizer.Typically for each spraying operation, the pressure used may be in therange of from about 1.5 to about 3.5 bar, such as about 2.5 bar, and thepump speed will vary depending on the viscosity of the sprayformulation. The pump speed maybe, for example, in the range of fromabout 2.5 to about 30 rpm, such as from about 5 to about 10 rpm. As anexample of this type of process, particles, such as fibers or powderparticulates, to be coated are stirred by a gas stream which alsoensures their drying (i.e., the evaporation of the organic solventand/or water). This method involves at least one coating, but mayinclude successive coatings, of the fibers with the spray formulation,followed by at least one drying operation to evaporate off the organicsolvent and/or water.

The cationically-charged material covalently bonds to the surfaces ofnaturally-derived particulates carrying surface hydroxyl groups, forexample, cellulose-based particulates. On the other hand, thecationically-charged material does not bond to, but coats, syntheticparticulates.

Optionally, one or more additional spray formulations, for example, asolution, a dispersion, or an emulsion, containing a film-formermaterial, may be introduced into the fluidizer while air is pumped intothe fluidizer chamber, so as to further coat the cationically-chargedfibers with the film-former finish material. The twice-coated fibers arethen dried again. The film former finish imparts hydrophobicity to thetreated fibers. In the case where naturally-derived particulates havingsurface hydroxyl groups are used, it is particularly useful that thecationically charged particulates receive a film former coating whichwill render the particulates hydrophobic.

Optionally, one or more additional coatings containing cationic and/oranionic material may be sprayed onto the particulates, prior to thecoating with film former, as long as the net final charge of theparticulates is cationic and is in the range of from about 0.1 mV toabout 400 mV. Each spraying step is followed by a drying step, prior tothe final coating with the film former material. The resultingparticulates are hydrophobic.

Using confocal microscopy, the inventors have determined ranges of theweight of the coating materials to the weight of the particulates usefulin carrying out the spray coating operations. Various ranges weretested, including 0.1:1, 0.25:1, 2.25:1, 3.75:1, 7.25:1, 10:1, 15:1 and30:1. It was observed that, for use as dry, treated particulatesintended for direct application to keratinous material, a useful rangeof the weight of the solution, dispersion, or emulsion containing thecharged coating material to the weight of the particulates in a spraycoating operation is in the range of from about 0.1:1 to about 2:1, suchas about 0.25:1. A ratio of less than about 0.1:1 is consideredundesirable, as such lesser amount would not sufficiently encapsulatethe particulates (i.e., the cationic charge would be too low to beuseful). The use of a ratio of greater than about 2:1 is also consideredundesirable as the additional layers of solution, dispersion or emulsioncontaining the charged coating material would result in flyaway of theparticulates due to the strong charges which begin to repel one another.In the case in which the dried, treated particulates are incorporatedinto a cosmetic base formula, such as a mascara composition, a broaderuseful range of the weight of the solution, dispersion, or emulsioncontaining the charged coating material to the weight of theparticulates was observed; the range being from about 0.1:1 to about5:1, such as about 0.25:1. A useful range of the weight of the solution,dispersion or emulsion containing the film former to the cationicallycharged particulates is from about 0.1:1 to about 30:1, such as about3.75:1. A lesser amount of the film former would not be expected toresult in dried, sufficiently coated cationically charged particulates.A greater amount of the film former would be too viscous and may resultin processing challenges, including clogging the spray apparatus of themicrofluidizer. In the case in which the dried, treated particulates areincorporated into a cosmetic base formula, such as a mascaracomposition, a broader useful range of the weight of the solution,dispersion, or emulsion containing the film former material wasobserved; the range being about 0.1:1 to about 60:1, such as from about0.1:1 to about 30:1, for example, about 3.75:1. A lower amount of filmformer would not be expected to provide sufficient coating to seal theprior coats onto the particulate surfaces and to impart hydrophobicityto the particulates. A greater amount of film former would result inoverly tacky particulates which would be expected to agglomerate in thebase formula.

Dry, treated particles according to the present invention may beprovided in a receptacle including a cap fitted with an applicator ofany type, such as a molded or a twisted wire brush, which would besuitable for loading product as it is withdrawn from the receptacle andfor depositing the particles on a keratinous surface, includingeyelashes, eyebrows or hair. The dry, treated particles may beencapsulated with at least one cationic coating, or with both a cationiccoating and a film forming coating, or with at least one cationiccoating, one or more additional anionic coatings, and a final filmformer finish. Cationically-charged fibers encapsulated with the filmformer are water-resistant.

Compositions of the present invention containing the dry, treatedparticulates, as described hereinabove, and a suitable vehicle, may alsobe provided in a receptacle described above for the dry, treatedparticles per se. Optional ingredients which may be formulated into thecompositions may include, but are not limited to, gellants, filmformers, pigments, moisturizers, emollients, humectants, preservatives,stabilizers, sequestering agents, and the like.

Treated particulate-containing compositions of the invention may takethe form of a mascara which incorporates the basic formulation elementsof a conventional mascara. Any type of mascara formulation would besuitable, including aqueous, single oil phase, water-in-oil oroil-in-water emulsions, and emulsions with three or more phases, withparticulates dispersed in the oil phase of the emulsions.

Dry, treated particulates prepared according to the present inventionmay be present in cosmetic formulations in amounts in the range of fromabout 0.1 to about 4 percent by total weight of the formulation.Preferably, the dry, treated particulates are present in amounts in therange of from about 0.4 to about 4 percent, such as from about 2 toabout 4 percent, by total weight of the formulation. Greater than about4 percent particulates by total weight of the formulation may beexpected to result in processing issues, including clogging ofequipment, and also non-uniform dispersion in the cosmetic formulationdue to agglomeration of the charged particulates.

In the case where the compositions are in the form of aqueous solutions,dispersions or emulsions, in addition to water the aqueous phase maycontain one or more aqueous phase structuring agents, that is, an agentthat increases the viscosity or, or thickens, the aqueous phase of thecomposition. This is particularly desirable when the composition is inthe form of a serum or gel. The aqueous phase structuring agent shouldbe compatible with the optically-activated systems, and also compatiblewith the other ingredients in the formulation. Suitable ranges ofaqueous phase structuring agent, if present, are from about 0.01 to 30%,preferably from about 0.1 to 20%, more preferably from about 0.5 to 15%by weight of the total composition. Examples of such agents includevarious acrylate based thickening agents, natural or synthetic gums,polysaccharides, and the like, including but not limited to those setforth below. As the optically-activated systems are in water solubleform, an aqueous phase thickening agent also contributes to stabilizingthis ingredient in the composition.

Polysaccharides may be suitable aqueous phase thickening agents.Examples of such polysaccharides include naturally derived materialssuch as agar, agarose, alicaligenes polysaccharides, algin, alginicacid, acacia gum, amylopectin, chitin, dextran, cassia gum, cellulosegum, gelatin, gellan gum, hyaluronic acid, hydroxyethyl cellulose,methyl cellulose, ethyl cellulose, pectin, sclerotium gum, xanthan gum,pectin, trehelose, gelatin, and so on.

Also suitable are different types of synthetic polymeric thickeners. Onetype includes acrylic polymeric thickeners comprised of monomers A and Bwherein A is selected from the group consisting of acrylic acid,methacrylic acid, and mixtures thereof; and B is selected from the groupconsisting of a C₁₋₂₂ alkyl acrylate, a C₁₋₂₂ alky methacrylate, andmixtures thereof are suitable. In one embodiment the A monomer comprisesone or more of acrylic acid or methacrylic acid, and the B monomer isselected from the group consisting of a C₁₋₁₀, most preferably C₁₋₄alkyl acrylate, a C₁₋₁₀, most preferably C₁₋₄ alkyl methacrylate, andmixtures thereof. Most preferably the B monomer is one or more of methylor ethyl acrylate or methacrylate. The acrylic copolymer may be suppliedin an aqueous solution having a solids content ranging from about10-60%, preferably 20-50%, more preferably 25-45% by weight of thepolymer, with the remainder water. The composition of the acryliccopolymer may contain from about 0.1-99 parts of the A monomer, andabout 0.1-99 parts of the B monomer. Acrylic polymer solutions includethose sold by Seppic, Inc., under the tradename Capigel.

Also suitable are acrylic polymeric thickeners that are copolymer of A,B, and C monomers wherein A and B are as defined above, and C has thegeneral formula:

wherein Z is —(CH₂)_(m); wherein m is 1-10, n is 2-3, o is 2-200, and Ris a C₁₀₋₃₀ straight or branched chain alkyl. Examples of the secondarythickening agent above, are copolymers where A and B are defined asabove, and C is CO, and wherein n, o, and R are as above defined.Examples of such secondary thickening agents includeacrylates/steareth-20 methacrylate copolymer, which is sold by Rohm &Haas under the tradename Acrysol ICS-1.

Also suitable are acrylate based anionic amphiphilic polymers containingat least one hydrophilic unit and at least one allyl ether unitcontaining a fatty chain. Preferred are those where the hydrophilic unitcontains an ethylenically unsaturated anionic monomer, more specificallya vinyl carboxylic acid such as acrylic acid, methacrylic acid ormixtures thereof, and where the allyl ether unit containing a fattychain corresponds to the monomer of formula:

CH₂═CR′CH₂OB_(n)R

in which R′ denotes H or CH₃, B denotes the ethylenoxy radical, n iszero or an integer ranging from 1 to 100, R denotes a hydrocarbonradical selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkylradicals which contain from 8 to 30 carbon atoms, preferably from 10 to24, and even more particularly from 12 to 18 carbon atoms. Morepreferred in this case is where R′ denotes H, n is equal to 10 and Rdenotes a stearyl (C18) radical. Anionic amphiphilic polymers of thistype are described and prepared in U.S. Pat. Nos. 4,677,152 and4,702,844, both of which are hereby incorporated by reference in theirentirety. Among these anionic amphiphilic polymers, polymers formed of20 to 60% by weight acrylic acid and/or methacrylic acid, of 5 to 60% byweight lower alkyl methacrylates, of 2 to 50% by weight allyl ethercontaining a fatty chain as mentioned above, and of 0 to 1% by weight ofa crosslinking agent which is a well-known copolymerizable polyethylenicunsaturated monomer, for instance diallyl phthalate, allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate andmethylenebisacrylamide. One commercial example of such polymers arecrosslinked terpolymers of methacrylic acid, of ethyl acrylate, ofpolyethylene glycol (having 10 EO units) ether of stearyl alcohol orsteareth-10, in particular those sold by the company Allied Colloidsunder the names SALCARE SC80 and SALCARE SC90, which are aqueousemulsions containing 30% of a crosslinked terpolymer of methacrylicacid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10).

Also suitable are acrylate copolymers such as Polyacrylate-3 which is acopolymer of methacrylic acid, methylmethacrylate, methylstyreneisopropylisocyanate, and PEG-40 behenate monomers; Polyacrylate-10 whichis a copolymer of sodium acryloyldimethyltaurate, sodium acrylate,acrylamide and vinyl pyrrolidone monomers; or Polyacrylate-11, which isa copolymer of sodium acryloyldimethylacryloyldimethyl taurate, sodiumacrylate, hydroxyethyl acrylate, lauryl acrylate, butyl acrylate, andacrylamide monomers.

Also suitable are crosslinked acrylate based polymers where one or moreof the acrylic groups may have substituted long chain alkyl (such as6-40, 10-30, and the like) groups, for example acrylates/C₁₀₋₃₀ alkylacrylate crosspolymer which is a copolymer of C₁₀₋₃₀ alkyl acrylate andone or more monomers of acrylic acid, methacrylic acid, or one of theirsimple esters crosslinked with the allyl ether of sucrose or the allylether of pentaerythritol. Such polymers are commonly sold under theCarbopol or Pemulen tradenames and have the CTFA name carbomer.

One particularly suitable type of aqueous phase thickening agent areacrylate based polymeric thickeners sold by Clariant under theAristoflex trademark such as Aristoflex AVC, which is ammoniumacryloyldimethyltaurate/VP copolymer; Aristoflex AVL which is the samepolymer has found in AVC dispersed in mixture containing caprylic/caprictriglyceride, trilaureth-4, and polyglyceryl-2 sesquiisostearate; orAristoflex HMB which is ammonium acryloyldimethyltaurate/beheneth-25methacrylate crosspolymer, and the like.

Also suitable as the aqueous phase thickening agents are variouspolyethylene glycols (PEG) derivatives where the degree ofpolymerization ranges from 1,000 to 200,000. Such ingredients areindicated by the designation “PEG” followed by the degree ofpolymerization in thousands, such as PEG-45M, which means PEG having45,000 repeating ethylene oxide units. Examples of suitable PEGderivatives include PEG 2M, 5M, 7M, 9M, 14M, 20M, 23M, 25M, 45M, 65M,90M, 115M, 160M, 180M, and the like.

Also suitable are polyglycerins which are repeating glycerin moietieswhere the number of repeating moieties ranges from 15 to 200, preferablyfrom about 20-100. Examples of suitable polyglycerins include thosehaving the CFTA names polyglycerin-20, polyglycerin-40, and the like.

In the event the compositions of the invention are in emulsion form, thecomposition will comprise an oil phase. Oily ingredients are desirablefor the skin moisturizing and protective properties. Oils, if present,will form a barrier on the skin so that the optically-activated complexpresent in the composition remains on the skin. Suitable oils includesilicones, esters, vegetable oils, synthetic oils, including but notlimited to those set forth herein. The oils may be volatile ornonvolatile, and are preferably in the form of a pourable liquid at roomtemperature. The term “volatile” means that the oil has a measurablevapor pressure, or a vapor pressure of at least about 2 mm. of mercuryat 20° C. The term “nonvolatile” means that the oil has a vapor pressureof less than about 2 mm. of mercury at 20° C.

Suitable volatile oils generally have a viscosity ranging from about 0.5to 5 centistokes 25° C. and include linear silicones, cyclic silicones,paraffinic hydrocarbons, or mixtures thereof. Volatile oils may be usedto promote more rapid drying of the skin care composition after it isapplied to skin. Volatile oils are more desirable when the skin careproducts containing the optically-activated complex are being formulatedfor consumers that have combination or oily skin. The term “combination”with respect to skin type means skin that is oily in some places on theface (such as the T-zone) and normal in others.

Cyclic silicones are one type of volatile silicone that may be used inthe composition. Such silicones have the general formula:

where n=3-6, preferably 4, 5, or 6.

Also suitable are linear volatile silicones, for example, those havingthe general formula:

(CH₃)₃Si—O—[Si(CH₃)₂—O]_(n)—Si(CH₃)₃

where n=0, 1, 2, 3, 4, or 5, preferably 0, 1, 2, 3, or 4.

Cyclic and linear volatile silicones are available from variouscommercial sources including Dow Corning Corporation and GeneralElectric. The Dow Corning linear volatile silicones are sold under thetradenames Dow Corning 244, 245, 344, and 200 fluids. These fluidsinclude hexamethyldisiloxane (viscosity 0.65 centistokes (abbreviatedcst)), octamethyltrisiloxane (1.0 cst), decamethyltetrasiloxane (1.5cst), dodecamethylpentasiloxane (2 cst) and mixtures thereof, with allviscosity measurements being at 25° C.

Suitable branched volatile silicones include alkyl trimethicones such asmethyl trimethicone, a branched volatile silicone having the generalformula:

Methyl trimethicone may be purchased from Shin-Etsu Silicones under thetradename TMF-1.5, having a viscosity of 1.5 centistokes at 25° C.

Also suitable as the volatile oils are various straight or branchedchain paraffinic hydrocarbons having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, or 20 carbon atoms, more preferably 8 to 16 carbonatoms. Suitable hydrocarbons include pentane, hexane, heptane, decane,dodecane, tetradecane, tridecane, and C₈₋₂₀ isoparaffins as disclosed inU.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are herebyincorporated by reference.

Preferred volatile paraffinic hydrocarbons have a molecular weight of70-225, preferably 160 to 190 and a boiling point range of 30 to 320,preferably 60 to 260° C., and a viscosity of less than about 10 cst. at25° C. Such paraffinic hydrocarbons are available from EXXON under theISOPARS trademark, and from the Permethyl Corporation. Suitable Cuisoparaffins are manufactured by Permethyl Corporation under thetradename Permethyl 99A. Various C₁₆ isoparaffins commerciallyavailable, such as isohexadecane (having the tradename Permethyl R), arealso suitable.

A variety of nonvolatile oils are also suitable for use in thecompositions of the invention. The nonvolatile oils generally have aviscosity of greater than about 5 to 10 centistokes at 25° C., and mayrange in viscosity up to about 1,000,000 centipoise at 25° C. Examplesof nonvolatile oils include, but are not limited to:

Suitable esters are mono-, di-, and triesters. The composition maycomprise one or more esters selected from the group, or mixturesthereof.

Monoesters are defined as esters formed by the reaction of amonocarboxylic acid having the formula R—COOH, wherein R is a straightor branched chain saturated or unsaturated alkyl having 2 to 45 carbonatoms, or phenyl; and an alcohol having the formula R—OH wherein R is astraight or branched chain saturated or unsaturated alkyl having 2-30carbon atoms, or phenyl. Both the alcohol and the acid may besubstituted with one or more hydroxyl groups. Either one or both of theacid or alcohol may be a “fatty” acid or alcohol, and may have fromabout 6 to 30 carbon atoms, more preferably 12, 14, 16, 18, or 22 carbonatoms in straight or branched chain, saturated or unsaturated form.Examples of monoester oils that may be used in the compositions of theinvention include hexyl laurate, butyl isostearate, hexadecylisostearate, cetyl palmitate, isostearyl neopentanoate, stearylheptanoate, isostearyl isononanoate, stearyl lactate, stearyl octanoate,stearyl stearate, isononyl isononanoate, and so on.

Suitable diesters are the reaction product of a dicarboxylic acid and analiphatic or aromatic alcohol or an aliphatic or aromatic alcohol havingat least two substituted hydroxyl groups and a monocarboxylic acid. Thedicarboxylic acid may contain from 2 to 30 carbon atoms, and may be inthe straight or branched chain, saturated or unsaturated form. Thedicarboxylic acid may be substituted with one or more hydroxyl groups.The aliphatic or aromatic alcohol may also contain 2 to 30 carbon atoms,and may be in the straight or branched chain, saturated, or unsaturatedform. Preferably, one or more of the acid or alcohol is a fatty acid oralcohol, i.e. contains 12-22 carbon atoms. The dicarboxylic acid mayalso be an alpha hydroxy acid. The ester may be in the dimer or trimerform. Examples of diester oils that may be used in the compositions ofthe invention include diisotearyl malate, neopentyl glycol dioctanoate,dibutyl sebacate, dicetearyl dimer dilinoleate, dicetyl adipate,diisocetyl adipate, diisononyl adipate, diisostearyl dimer dilinoleate,diisostearyl fumarate, diisostearyl malate, dioctyl malate, and so on.

Suitable triesters comprise the reaction product of a tricarboxylic acidand an aliphatic or aromatic alcohol or alternatively the reactionproduct of an aliphatic or aromatic alcohol having three or moresubstituted hydroxyl groups with a monocarboxylic acid. As with themono- and diesters mentioned above, the acid and alcohol contain 2 to 30carbon atoms, and may be saturated or unsaturated, straight or branchedchain, and may be substituted with one or more hydroxyl groups.Preferably, one or more of the acid or alcohol is a fatty acid oralcohol containing 12 to 22 carbon atoms. Examples of triesters includeesters of arachidonic, citric, or behenic acids, such as triarachidin,tributyl citrate, triisostearyl citrate, tri C₁₂₋₁₃ alkyl citrate,tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecylcitrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate,and so on.

Esters suitable for use in the composition are further described in theC.T.F.A. Cosmetic Ingredient Dictionary and Handbook, Eleventh Edition,2006, under the classification of “Esters”, the text of which is herebyincorporated by reference in its entirety.

It may be desirable to incorporate one or more nonvolatile hydrocarbonoils into the composition. Suitable nonvolatile hydrocarbon oils includeparaffinic hydrocarbons and olefins, preferably those having greaterthan about 20 carbon atoms. Examples of such hydrocarbon oils includeC₂₄₋₂₈ olefins, C₃₀₋₄₅ olefins, C₂₀₋₄₀ isoparaffins, hydrogenatedpolyisobutene, polyisobutene, polydecene, hydrogenated polydecene,mineral oil, pentahydrosqualene, squalene, squalane, and mixturesthereof. In one preferred embodiment such hydrocarbons have a molecularweight ranging from about 300 to 1000 Daltons.

Synthetic or naturally occurring glyceryl esters of fatty acids, ortriglycerides, are also suitable for use in the compositions. Bothvegetable and animal sources may be used. Examples of such oils includecastor oil, lanolin oil, C₁₀₋₁₈ triglycerides,caprylic/capric/triglycerides, sweet almond oil, apricot kernel oil,sesame oil, camelina sativa oil, tamanu seed oil, coconut oil, corn oil,cottonseed oil, linseed oil, ink oil, olive oil, palm oil, illipebutter, rapeseed oil, soybean oil, grapeseed oil, sunflower seed oil,walnut oil, and the like.

Also suitable are synthetic or semi-synthetic glyceryl esters, such asfatty acid mono-, di-, and triglycerides which are natural fats or oilsthat have been modified, for example, mono-, di- or triesters of polyolssuch as glycerin. In an example, a fatty (C₁₂₋₂₂) carboxylic acid isreacted with one or more repeating glyceryl groups. glyceryl stearate,diglyceryl diiosostearate, -3-3 isostearate, polyglyceryl-4 isostearate,polyglyceryl-6 ricinoleate, glyceryl dioleate, glyceryl diisotearate,glyceryl tetraisostearate, glyceryl trioctanoate, diglyceryl distearate,glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castoroils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryltallowates, and so on.

Nonvolatile silicone oils, both water soluble and water insoluble, arealso suitable for use in the composition. Such silicones preferably havea viscosity ranging from about greater than 5 to 800,000 cst, preferably20 to 200,000 cst at 25° C. Suitable water insoluble silicones includeamine functional silicones such as amodimethicone.

For example, such nonvolatile silicones may have the following generalformula:

wherein R and R′ are each independently C₁₋₃₀ straight or branchedchain, saturated or unsaturated alkyl, phenyl or aryl, trialkylsiloxy,and x and y are each independently 1-1,000,000; with the proviso thatthere is at least one of either x or y, and A is alkyl siloxy endcapunit. Preferred is where A is a methyl siloxy endcap unit; in particulartrimethylsiloxy, and R and R′ are each independently a C₁₋₃₀ straight orbranched chain alkyl, phenyl, or trimethylsiloxy, more preferably aC₁₋₂₂ alkyl, phenyl, or trimethylsiloxy, most preferably methyl, phenyl,or trimethylsiloxy, and resulting silicone is dimethicone, phenyldimethicone, diphenyl dimethicone, phenyl trimethicone, ortrimethylsiloxyphenyl dimethicone. Other examples include alkyldimethicones such as cetyl dimethicone, and the like wherein at leastone R is a fatty alkyl (C₁₂, C₁₄, C₁₆, C₁₈, C₂₀, or C₂₂), and the otherR is methyl, and A is a trimethylsiloxy endcap unit, provided such alkyldimethicone is a pourable liquid at room temperature. Phenyltrimethicone can be purchased from Dow Corning Corporation under thetradename 556 Fluid. Trimethylsiloxyphenyl dimethicone can be purchasedfrom Wacker-Chemie under the tradename PDM-1000. Cetyl dimethicone, alsoreferred to as a liquid silicone wax, may be purchased from Dow Corningas Fluid 2502, or from DeGussa Care & Surface Specialties under thetrade names Abil Wax 9801, or 9814.

Various types of fluorinated oils may also be suitable for use in thecompositions including but not limited to fluorinated silicones,fluorinated esters, or perfluropolyethers. Particularly suitable arefluorosilicones such as trimethylsilyl endcapped fluorosilicone oil,polytrifluoropropylmethylsiloxanes, and similar silicones such as thosedisclosed in U.S. Pat. No. 5,118,496 which is hereby incorporated byreference. Perfluoropolyethers include those disclosed in U.S. Pat. Nos.5,183,589, 4,803,067, 5,183,588 all of which are hereby incorporated byreference, which are commercially available from Montefluos under thetrademark Fomblin.

In the case where the composition is anhydrous or in the form of anemulsion, it may be desirable to include one or more oil phasestructuring agents in the cosmetic composition. The term “oil phasestructuring agent” means an ingredient or combination of ingredients,soluble or dispersible in the oil phase, which will increase theviscosity, or structure, the oil phase. The oil phase structuring agentis compatible with the optically-activated complex, particularly if theoptically-activated complex may be solubilized in the nonpolar oilsforming the oil phase of the composition. The term “compatible” meansthat the oil phase structuring agent and optically-activated complex arecapable of being formulated into a cosmetic product that is generallystable. The structuring agent may be present in an amount sufficient toprovide a liquid composition with increased viscosity, a semi-solid, orin some cases a solid composition that may be self-supporting. Thestructuring agent itself may be present in the liquid, semi-solid, orsolid form. Suggested ranges of structuring agent are from about 0.01 to70%, preferably from about 0.05 to 50%, more preferably from about0.1-35% by weight of the total composition. Suitable oil phasestructuring agents include those that are silicone based or organicbased. They may be polymers or non-polymers, synthetic, natural, or acombination of both.

A variety of oil phase structuring agents may be silicone based, such assilicone elastomers, silicone gums, silicone waxes, linear siliconeshaving a degree of polymerization that provides the silicone with adegree of viscosity such that when incorporated into the cosmeticcomposition it is capable of increasing the viscosity of the oil phase.Examples of silicone structuring agents include, but are not limited tothe following.

Silicone elastomers suitable for use in the compositions of theinvention include those that are formed by addition reaction-curing, byreacting an SiH-containing diorganosiloxane and an organopolysiloxanehaving terminal olefinic unsaturation, or an alpha-omega dienehydrocarbon, in the presence of a platinum metal catalyst. Suchelastomers may also be formed by other reaction methods such ascondensation-curing organopolysiloxane compositions in the presence ofan organotin compound via a dehydrogenation reaction betweenhydroxyl-terminated diorganopolysiloxane and SiH-containingdiorganopolysiloxane or alpha omega diene; or by condensation-curingorganopolysiloxane compositions in the presence of an organotin compoundor a titanate ester using a condensation reaction between anhydroxyl-terminated diorganopolysiloxane and a hydrolysableorganosiloxane; peroxide-curing organopolysiloxane compositions whichthermally cure in the presence of an organoperoxide catalyst.

One type of elastomer that may be suitable is prepared by additionreaction-curing an organopolysiloxane having at least 2 lower alkenylgroups in each molecule or an alpha-omega diene; and anorganopolysiloxane having at least 2 silicon-bonded hydrogen atoms ineach molecule; and a platinum-type catalyst. While the lower alkenylgroups such as vinyl, can be present at any position in the molecule,terminal olefinic unsaturation on one or both molecular terminals ispreferred. The molecular structure of this component may be straightchain, branched straight chain, cyclic, or network. Theseorganopolysiloxanes are exemplified by methylvinylsiloxanes,methylvinylsiloxane-dimethylsiloxane copolymers,dimethylvinylsiloxy-terminated dimethylpolysiloxanes,dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxanecopolymers, dimethylvinylsiloxy-terminateddimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers,trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxanecopolymers, trimethylsiloxy-terminateddimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers,dimethylvinylsiloxy-terminated methyl(3,3,3-trifluoropropyl)polysiloxanes, and dimethylvinylsiloxy-terminateddimethylsiloxane-methyl(3,3,-trifluoropropyl)siloxane copolymers,decadiene, octadiene, heptadiene, hexadiene, pentadiene, or tetradiene,or tridiene.

Curing proceeds by the addition reaction of the silicon-bonded hydrogenatoms in the dimethyl methylhydrogen siloxane, with the siloxane oralpha-omega diene under catalysis using the catalyst mentioned herein.To form a highly crosslinked structure, the methyl hydrogen siloxanemust contain at least 2 silicon-bonded hydrogen atoms in each moleculein order to optimize function as a crosslinker.

The catalyst used in the addition reaction of silicon-bonded hydrogenatoms and alkenyl groups, and is concretely exemplified bychloroplatinic acid, possibly dissolved in an alcohol or ketone and thissolution optionally aged, chloroplatinic acid-olefin complexes,chloroplatinic acid-alkenylsiloxane complexes, chloroplatinicacid-diketone complexes, platinum black, and carrier-supported platinum.

Examples of suitable silicone elastomers for use in the compositions ofthe invention may be in the powder form, or dispersed or solubilized insolvents such as volatile or non-volatile silicones, or siliconecompatible vehicles such as paraffinic hydrocarbons or esters. Examplesof silicone elastomer powders include vinyl dimethicone/methiconesilesquioxane crosspolymers like Shin-Etsu's KSP-100, KSP-101, KSP-102,KSP-103, KSP-104, KSP-105, hybrid silicone powders that contain afluoroalkyl group like Shin-Etsu's KSP-200 which is a fluoro-siliconeelastomer, and hybrid silicone powders that contain a phenyl group suchas Shin-Etsu's KSP-300, which is a phenyl substituted siliconeelastomer; and Dow Corning's DC 9506. Examples of silicone elastomerpowders dispersed in a silicone compatible vehicle includedimethicone/vinyl dimethicone crosspolymers supplied by a variety ofsuppliers including Dow Corning Corporation under the tradenames 9040 or9041, GE Silicones under the tradename SFE 839, or Shin-Etsu Siliconesunder the tradenames KSG-15, 16, 18. KSG-15 has the CTFA namecyclopentasiloxane/dimethicone/vinyl dimethicone crosspolymer. KSG-18has the INCI name phenyl trimethicone/dimethicone/phenyl vinyldimethicone crossoplymer. Silicone elastomers may also be purchased fromGrant Industries under the Gransil trademark. Also suitable are siliconeelastomers having long chain alkyl substitutions such as lauryldimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu underthe tradenames KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44.Cross-linked organopolysiloxane elastomers useful in the presentinvention and processes for making them are further described in U.S.Pat. No. 4,970,252 to Sakuta et al., issued Nov. 13, 1990; U.S. Pat. No.5,760,116 to Kilgour et al., issued Jun. 2, 1998; U.S. Pat. No.5,654,362 to Schulz, Jr. et al. issued Aug. 5, 1997; and Japanese PatentApplication JP 61-18708, assigned to Pola Kasei Kogyo KK, each of whichare herein incorporated by reference in its entirety. It is particularlydesirable to incorporate silicone elastomers into the compositions ofthe invention because they provide excellent “feel” to the composition,are very stable in cosmetic formulations, and relatively inexpensive.

Also suitable for use as an oil phase structuring agent are one or moresilicone gums. The term “gum” means a silicone polymer having a degreeof polymerization sufficient to provide a silicone having a gum-liketexture. In certain cases the silicone polymer forming the gum may becrosslinked. The silicone gum typically has a viscosity ranging fromabout 500,000 to 100 million cst at 25° C., preferably from about600,000 to 20 million, more preferably from about 600,000 to 12 millioncst. All ranges mentioned herein include all subranges, e.g. 550,000;925,000; 3.5 million.

The silicone gums that are used in the compositions include, but are notlimited to, those of the general formula:

wherein R₁ to R₉ are each independently an alkyl having 1 to 30 carbonatoms, aryl, or aralkyl; and X is OH or a C₁₋₃₀ alkyl, or vinyl; andwherein x, y, or z may be zero with the proviso that no more than two ofx, y, or z are zero at any one time, and further that x, y, and z aresuch that the silicone gum has a viscosity of at least about 500,000cst, ranging up to about 100 million centistokes at 25° C. Preferred iswhere R is methyl or OH.

Such silicone gums may be purchased in pure form from a variety ofsilicone manufacturers including Wacker-Chemie or Dow Corning, and thelike. Such silicone gums include those sold by Wacker-Belsil under thetrade names CM3092, Wacker-Belsil 1000, or Wacker-Belsil DM 3096. Asilicone gum where X is OH, also referred to as dimethiconol, isavailable from Dow Corning Corporation under the trade name 1401. Thesilicone gum may also be purchased in the form of a solution ordispersion in a silicone compatible vehicle such as volatile ornonvolatile silicone. An example of such a mixture may be purchased fromBarnet Silicones under the HL-88 tradename, having the INCI namedimethicone.

Another type of oily phase structuring agent includes silicone waxesthat are typically referred to as alkyl silicone waxes which aresemi-solids or solids at room temperature. The term “alkyl silicone wax”means a polydimethylsiloxane having a substituted long chain alkyl (suchas C16 to 30) that confers a semi-solid or solid property to thesiloxane. Examples of such silicone waxes include stearyl dimethicone,which may be purchased from DeGussa Care & Surface Specialties under thetradename Abil Wax 9800 or from Dow Corning under the tradename 2503.Another example is bis-stearyl dimethicone, which may be purchased fromGransil Industries under the tradename Gransil A-18, or behenyldimethicone, behenoxy dimethicone.

Also suitable as oil phase structuring agents are various types ofpolymeric compounds such as polyamides or silicone polyamides.

The term silicone polyamide means a polymer comprised of siliconemonomers and monomers containing amide groups as further describedherein. The silicone polyamide preferably comprises moieties of thegeneral formula:

wherein X is a linear or branched alkylene having from about 1-30 carbonatoms; R₁, R₂, R₃, and R₄ are each independently C₁₋₃₀ straight orbranched chain alkyl which may be substituted with one or more hydroxylor halogen groups; phenyl which may be substituted with one or moreC₁₋₃₀ alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxanechain having the general formula:

and Y is:

-   -   (a) a linear or branched alkylene having from about 1-40 carbon        atoms which may be substituted with:        -   (i) one or more amide groups having the general formula            R₁CONR₁, or        -   (ii) C₅₋₆ cyclic ring, or        -   (iii) phenylene which may be substituted with one or more            C₁₋₁₀ alkyl groups, or        -   (iv) hydroxy, or        -   (v) C₃₋₈ cycloalkane, or        -   (vi) C₁₋₂₀ alkyl which may be substituted with one or more            hydroxy groups, or        -   (vii) C₁₋₁₀ alkyl amines; or    -   (b) TR₅R₆R₇        wherein R₅, R₆, and R₇, are each independently a C₁₋₁₀ linear or        branched alkylenes, and T is CR₈ wherein R₈ is hydrogen, a        trivalent atom N, P, or Al, or a C₁₋₃₀ straight or branched        chain alkyl which may be substituted with one or more hydroxyl        or halogen groups; phenyl which may be substituted with one or        more C₁₋₃₀ alkyl groups, halogen, hydroxyl, or alkoxy groups; or        a siloxane chain having the general formula:

Preferred is where R₁, R₂, R₃, and R₄ are C₁₋₁₀, preferably methyl; andX and Y is a linear or branched alkylene. Preferred are siliconepolyamides having the general formula:

wherein a and b are each independently sufficient to provide a siliconepolyamide polymer having a melting point ranging from about 60 to 120°C., and a molecular weight ranging from about 40,000 to 500,000 Daltons.One type of silicone polyamide that may be used in the compositions ofthe invention may be purchased from Dow Corning Corporation under thetradename Dow Corning 2-8178 gellant which has the CTFA namenylon-611/dimethicone copolymer which is sold in a compositioncontaining PPG-3 myristyl ether.Also suitable are polyamides such as those purchased from ArizonaChemical under the tradenames Uniclear and Sylvaclear. Such polyamidesmay be ester terminated or amide terminated. Examples of esterterminated polyamides include, but are not limited to those having thegeneral formula:

wherein n denotes a number of amide units such that the number of estergroups ranges from about 10% to 50% of the total number of ester andamide groups; each R¹ is independently an alkyl or alkenyl groupcontaining at least 4 carbon atoms; each R² is independently a C₄₋₄₂hydrocarbon group, with the proviso that at least 50% of the R² groupsare a C₃₀₋₄₂ hydrocarbon; each R³ is independently an organic groupcontaining at least 2 carbon atoms, hydrogen atoms and optionally one ormore oxygen or nitrogen atoms; and each R⁴ is independently a hydrogenatom, a C₁₋₁₀ alkyl group or a direct bond to R³ or to another R⁴, suchthat the nitrogen atom to which R³ and R⁴ are both attached forms partof a heterocyclic structure defined by R⁴—N—R³, with at least 50% of thegroups R₄ representing a hydrogen atom.

General examples of ester and amide terminated polyamides that may beused as oil phase gelling agents include those sold by Arizona Chemicalunder the tradenames Sylvaclear A200V or A2614V, both having the CTFAname ethylenediamine/hydrogenated dimer dilinoleatecopolymer/bis-di-C₁₄₋₁₈ alkyl amide; Sylvaclear AF1900V; Sylvaclear C75Vhaving the CTFA name bis-stearyl ethylenediamine/neopentylglycol/stearyl hydrogenated dimer dilinoleate copolymer; SylvaclearPA1200V having the CTFA name Polyamide-3; Sylvaclear PE400V; SylvaclearWF1500V; or Uniclear, such as Uniclear 100VG having the INCI nameethylenediamine/stearyl dimer dilinoleate copolymer; orethylenediamine/stearyl dimer ditallate copolymer. Other examples ofsuitable polyamides include those sold by Henkel under the Versamidtrademark (such as Versamid 930, 744, 1655), or by Olin MathiesonChemical Corp. under the brand name Onamid S or Onamid C.

Also suitable as the oil phase structuring agent may be one or morenatural or synthetic waxes such as animal, vegetable, or mineral waxes.Preferably such waxes will have a higher melting point such as fromabout 50 to 150° C., more preferably from about 65 to 100° C. Examplesof such waxes include waxes made by Fischer-Tropsch synthesis, such aspolyethylene or synthetic wax; or various vegetable waxes such asbayberry, candelilla, ozokerite, acacia, beeswax, ceresin, cetyl esters,flower wax, citrus wax, carnauba wax, jojoba wax, japan wax,polyethylene, microcrystalline, rice bran, lanolin wax, mink, montan,bayberry, ouricury, ozokerite, palm kernel wax, paraffin, avocado wax,apple wax, shellac wax, clary wax, spent grain wax, grape wax, andpolyalkylene glycol derivatives thereof such as PEG6-20 beeswax, orPEG-12 carnauba wax; or fatty acids or fatty alcohols, including estersthereof, such as hydroxystearic acids (for example 12-hydroxy stearicacid), tristearin, tribehenin, and so on.

One type of structuring agent that may be used in the compositioncomprises natural or synthetic montmorillonite minerals such ashectorite, bentonite, and quaternized derivatives thereof, which areobtained by reacting the minerals with a quaternary ammonium compound,such as stearalkonium bentonite, hectorites, quaternized hectorites suchas Quaternium-18 hectorite, attapulgite, carbonates such as propylenecarbonate, bentones, and the like.

Another type of structuring agent that may be used in the compositionsare silicas, silicates, silica silylate, and alkali metal or alkalineearth metal derivatives thereof. These silicas and silicates aregenerally found in the particulate form and include silica, silicasilylate, magnesium aluminum silicate, and the like.

The composition may contain one or more surfactants, especially if inthe emulsion form. However, such surfactants may be used if thecompositions are anhydrous also, and will assist in dispersingingredients that have polarity, for example pigments. Such surfactantsmay be silicone or organic based. The surfactants will aid in theformation of stable emulsions of either the water-in-oil or oil-in-waterform. If present, the surfactant may range from about 0.001 to 30%,preferably from about 0.005 to 25%, more preferably from about 0.1 to20% by weight of the total composition.

Suitable silicone surfactants include polyorganosiloxane polymers thathave amphiphilic properties, for example contain hydrophilic radicalsand lipophilic radicals. These silicone surfactants may be liquids orsolids at room temperature.

One type of silicone surfactant that may be used is generally referredto as dimethicone copolyol or alkyl dimethicone copolyol. Thissurfactant is either a water-in-oil or oil-in-water surfactant having anHydrophile/Lipophile Balance (HLB) ranging from about 2 to 18.Preferably the silicone surfactant is a nonionic surfactant having anHLB ranging from about 2 to 12, preferably about 2 to 10, mostpreferably about 4 to 6. The term “hydrophilic radical” means a radicalthat, when substituted onto the organosiloxane polymer backbone, confershydrophilic properties to the substituted portion of the polymer.Examples of radicals that will confer hydrophilicity arehydroxy-polyethyleneoxy, hydroxyl, carboxylates, and mixtures thereof.The term “lipophilic radical” means an organic radical that, whensubstituted onto the organosiloxane polymer backbone, confers lipophilicproperties to the substituted portion of the polymer. Examples oforganic radicals that will confer lipophilicity are C₁₋₄₀ straight orbranched chain alkyl, fluoro, aryl, aryloxy, C₁₋₄₀ hydrocarbyl acyl,hydroxy-polypropyleneoxy, or mixtures thereof.

One type of suitable silicone surfactant has the general formula:

wherein p is 0-40 (the range including all numbers between and subrangessuch as 2, 3, 4, 13, 14, 15, 16, 17, 18, etc.), and PE is(—C₂H₄O)_(n)—(—C₃H₆O)_(b)—H wherein a is 0 to 25, b is 0-25 with theproviso that both a and b cannot be 0 simultaneously, x and y are eachindependently ranging from 0 to 1 million with the proviso that theyboth cannot be 0 simultaneously. In one preferred embodiment, x, y, z,a, and b are such that the molecular weight of the polymer ranges fromabout 5,000 to about 500,000, more preferably from about 10,000 to100,000, and is most preferably approximately about 50,000 and thepolymer is generically referred to as dimethicone copolyol.

One type of silicone surfactant is wherein p is such that the long chainalkyl is cetyl or lauryl, and the surfactant is called, generically,cetyl dimethicone copolyol or lauryl dimethicone copolyol respectively.

In some cases the number of repeating ethylene oxide or propylene oxideunits in the polymer are also specified, such as a dimethicone copolyolthat is also referred to as PEG-15/PPG-10 dimethicone, which refers to adimethicone having substituents containing 15 ethylene glycol units and10 propylene glycol units on the siloxane backbone. It is also possiblefor one or more of the methyl groups in the above general structure tobe substituted with a longer chain alkyl (e.g. ethyl, propyl, butyl,etc.) or an ether such as methyl ether, ethyl ether, propyl ether, butylether, and the like.

Examples of silicone surfactants are those sold by Dow Corning under thetradename Dow Corning 3225C Formulation Aid having the CTFA namecyclotetrasiloxane (and) cyclopentasiloxane (and) PEG/PPG-18dimethicone; or 5225C Formulation Aid, having the CTFA namecyclopentasiloxane (and) PEG/PPG-18/18 dimethicone; or Dow Corning 190Surfactant having the CTFA name PEG/PPG-18/18 dimethicone; or DowCorning 193 Fluid, Dow Corning 5200 having the CTFA name laurylPEG/PPG-18/18 methicone; or Abil EM 90 having the CTFA name cetylPEG/PPG-14/14 dimethicone sold by Goldschmidt; or Abil EM 97 having theCTFA name bis-cetyl PEG/PPG-14/14 dimethicone sold by Goldschmidt; orAbil WE 09 having the CTFA name cetyl PEG/PPG-10/1 dimethicone in amixture also containing polyglyceryl-4 isostearate and hexyl laurate; orKF-6011 sold by Shin-Etsu Silicones having the CTFA name PEG-11 methylether dimethicone; KF-6012 sold by Shin-Etsu Silicones having the CTFAname PEG/PPG-20/22 butyl ether dimethicone; or KF-6013 sold by Shin-EtsuSilicones having the CTFA name PEG-9 dimethicone; or KF-6015 sold byShin-Etsu Silicones having the CTFA name PEG-3 dimethicone; or KF-6016sold by Shin-Etsu Silicones having the CTFA name PEG-9 methyl etherdimethicone; or KF-6017 sold by Shin-Etsu Silicones having the CTFA namePEG-10 dimethicone; or KF-6038 sold by Shin-Etsu Silicones having theCTFA name lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

Also suitable are various types of crosslinked silicone surfactants thatare often referred to as emulsifying elastomers. They are typicallyprepared as set forth above with respect to the section “siliconeelastomers” except that the silicone elastomers will contain at leastone hydrophilic moiety such as polyoxyalkylenated groups. Typicallythese polyoxyalkylenated silicone elastomers are crosslinkedorganopolysiloxanes that may be obtained by a crosslinking additionreaction of diorganopolysiloxane comprising at least one hydrogen bondedto silicon and of a polyoxyalkylene comprising at least twoethylenically unsaturated groups. In at least one embodiment, thepolyoxyalkylenated crosslinked organo-polysiloxanes are obtained by acrosslinking addition reaction of a diorganopolysiloxane comprising atleast two hydrogens each bonded to a silicon, and a polyoxyalkylenecomprising at least two ethylenically unsaturated groups, optionally inthe presence of a platinum catalyst, as described, for example, in U.S.Pat. No. 5,236,986 and U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793and U.S. Pat. No. 5,811,487, the contents of which are incorporated byreference.

Polyoxyalkylenated silicone elastomers that may be used in at least oneembodiment of the invention include those sold by Shin-Etsu Siliconesunder the names KSG-21, KSG-20, KSG-30, KSG-31, KSG-32, KSG-33; KSG-210which is dimethicone/PEG-10/15 crosspolymer dispersed in dimethicone;KSG-310 which is PEG-15 lauryl dimethicone crosspolymer; KSG-320 whichis PEG-15 lauryl dimethicone crosspolymer dispersed in isododecane;KSG-330 (the former dispersed in triethylhexanoin), KSG-340 which is amixture of PEG-10 lauryl dimethicone crosspolymer and PEG-15 lauryldimethicone crosspolymer.

Also suitable are polyglycerolated silicone elastomers like thosedisclosed in PCT/WO 2004/024798, which is hereby incorporated byreference in its entirety. Such elastomers include Shin-Etsu's KSGseries, such as KSG-710 which is dimethicone/polyglycerin-3 crosspolymerdispersed in dimethicone; or lauryl dimethicone/polyglycerin-3crosspolymer dispersed in a variety of solvent such as isododecane,dimethicone, triethylhexanoin, sold under the Shin-Etsu tradenamesKSG-810, KSG-820, KSG-830, or KSG-840. Also suitable are silicones soldby Dow Corning under the tradenames 9010 and DC9011. One preferredcrosslinked silicone elastomer emulsifier is dimethicone/PEG-10/15crosspolymer, which provides excellent aesthetics due to its elastomericbackbone, but also surfactancy properties.

The composition may comprise one or more nonionic organic surfactants.Suitable nonionic surfactants include alkoxylated alcohols, or ethers,formed by the reaction of an alcohol with an alkylene oxide, usuallyethylene or propylene oxide. Preferably the alcohol is either a fattyalcohol having 6 to 30 carbon atoms. Examples of such ingredientsinclude Steareth 2-100, which is formed by the reaction of stearylalcohol and ethylene oxide and the number of ethylene oxide units rangesfrom 2 to 100; Beheneth 5-30 which is formed by the reaction of behenylalcohol and ethylene oxide where the number of repeating ethylene oxideunits is 5 to 30; Ceteareth 2-100, formed by the reaction of a mixtureof cetyl and stearyl alcohol with ethylene oxide, where the number ofrepeating ethylene oxide units in the molecule is 2 to 100; Ceteth 1-45which is formed by the reaction of cetyl alcohol and ethylene oxide, andthe number of repeating ethylene oxide units is 1 to 45, and so on.

Other alkoxylated alcohols are formed by the reaction of fatty acids andmono-, di- or polyhydric alcohols with an alkylene oxide. For example,the reaction products of C₆₋₃₀ fatty carboxylic acids and polyhydricalcohols which are monosaccharides such as glucose, galactose, methylglucose, and the like, with an alkoxylated alcohol. Examples includepolymeric alkylene glycols reacted with glyceryl fatty acid esters suchas PEG glyceryl oleates, PEG glyceryl stearate; or PEGpolyhydroxyalkanotes such as PEG dipolyhydroxystearate wherein thenumber of repeating ethylene glycol units ranges from 3 to 1000.

Also suitable as nonionic surfactants are formed by the reaction of acarboxylic acid with an alkylene oxide or with a polymeric ether. Theresulting products have the general formula:

where RCO is the carboxylic ester radical, X is hydrogen or lower alkyl,and n is the number of polymerized alkoxy groups. In the case of thediesters, the two RCO-groups do not need to be identical. Preferably, Ris a C6-30 straight or branched chain, saturated or unsaturated alkyl,and n is from 1-100.

Monomeric, homopolymeric, or block copolymeric ethers are also suitableas nonionic surfactants. Typically, such ethers are formed by thepolymerization of monomeric alkylene oxides, generally ethylene orpropylene oxide. Such polymeric ethers have the following generalformula:

wherein R is H or lower alkyl and n is the number of repeating monomerunits, and ranges from 1 to 500.

Other suitable nonionic surfactants include alkoxylated sorbitan andalkoxylated sorbitan derivatives. For example, alkoxylation, inparticular ethoxylation of sorbitan provides polyalkoxylated sorbitanderivatives. Esterification of polyalkoxylated sorbitan providessorbitan esters such as the polysorbates. For example, thepolyalkyoxylated sorbitan can be esterified with C₆₋₃₀, preferablyC₁₂₋₂₂ fatty acids. Examples of such ingredients include Polysorbates20-85, sorbitan oleate, sorbitan sesquioleate, sorbitan palmitate,sorbitan sesquiisostearate, sorbitan stearate, and so on.

Certain types of amphoteric, zwitterionic, or cationic surfactants mayalso be used in the compositions. Descriptions of such surfactants areset forth in U.S. Pat. No. 5,843,193, which is hereby incorporated byreference in its entirety.

It may also be desirable to include one or more humectants in thecomposition. If present, such humectants may range from about 0.001 to25%, preferably from about 0.005 to 20%, more preferably from about 0.1to 15% by weight of the total composition. Examples of suitablehumectants include glycols, sugars, and the like. Suitable glycols arein monomeric or polymeric form and include polyethylene andpolypropylene glycols such as PEG 4-200, which are polyethylene glycolshaving from 4 to 200 repeating ethylene oxide units; as well as C₁₋₆alkylene glycols such as propylene glycol, butylene glycol, pentyleneglycol, and the like. Suitable sugars, some of which are also polyhydricalcohols, are also suitable humectants. Examples of such sugars includeglucose, fructose, honey, hydrogenated honey, inositol, maltose,mannitol, maltitol, sorbitol, sucrose, xylitol, xylose, and so on. Alsosuitable is urea.

It may be desirable to include one or more botanical extracts in thecompositions. If so, suggested ranges are from about 0.0001 to 10%,preferably about 0.0005 to 8%, more preferably about 0.001 to 5% byweight of the total composition. Suitable botanical extracts includeextracts from plants (herbs, roots, flowers, fruits, seeds) such asflowers, fruits, vegetables, and so on, including yeast ferment extract,Padina Pavonica extract, thermus thermophilis ferment extract, camelinasativa seed oil, boswellia serrata extract, olive extract, AribodopsisThaliana extract, Acacia Dealbata extract, Acer Saccharinum (sugarmaple), acidopholus, acorus, aesculus, agaricus, agave, agrimonia,algae, aloe, citrus, brassica, cinnamon, orange, apple, blueberry,cranberry, peach, pear, lemon, lime, pea, seaweed, caffeine, green tea,chamomile, willowbark, mulberry, poppy, whey protein, and those setforth on pages 1646 through 1660 of the CTFA Cosmetic IngredientHandbook, Eighth Edition, Volume 2. Further specific examples include,but are not limited to, Camelia sinensis, Siegesbeckia orientalis,Glycyrrhiza Glabra, Salix Nigra, Macrocycstis Pyrifera, Pyrus Malus,Saxifraga Sarmentosa, Vitis Vinifera, Morus Nigra, ScutellariaBaicalensis, Anthemis Nobilis, Salvia Sclarea, Rosmarinus Officianalis,Citrus Medica Limonum, Panax Ginseng, Siegesbeckia Orientalis, FructusMume, Ascophyllum Nodosum, Bifida Ferment lysate, Saccharomyces lysate,Glycine Soja extract, Beta Vulgaris, Haberlea Rhodopensis, PolygonumCuspidatum, Citrus Aurantium Dulcis, Vitis Vinifera, SelaginellaTamariscina, Humulus Lupulus, Citrus Reticulata Peel, Punica Granatum,Asparagopsis, Curcuma Longa, Menyanthes Trifoliata, Helianthus Annuus,Triticum vulgare, Hordeum Vulgare, Cucumis Sativus, Evernia Prunastri,Evernia Furfuracea, and mixtures thereof.

It may also be desirable to include one or more sunscreens in thecompositions of the invention. Such sunscreens include chemical UVA orUVB sunscreens or physical sunscreens in the particulate form. Inclusionof sunscreens in the compositions containing the optically-activatedcomplex will provide additional protection to skin during daylighthours.

If desired, the composition may comprise one or more UVA sunscreens. Theterm “UVA sunscreen” means a chemical compound that blocks UV radiationin the wavelength range of about 320 to 400 nm. Preferred UVA sunscreensare dibenzoylmethane compounds having the general formula:

wherein R₁ is H, OR and NRR wherein each R is independently H, C₁₋₂₀straight or branched chain alkyl; R₂ is H or OH; and R₃ is H, C₁₋₂₀straight or branched chain alkyl.

Preferred is where R₁ is OR where R is a C₁₋₂₀ straight or branchedalkyl, preferably methyl; R₂ is H; and R₃ is a C₁₋₂₀ straight orbranched chain alkyl, more preferably, butyl.

Examples of suitable UVA sunscreen compounds of this general formulainclude 4-methyldibenzoylmethane, 2-methyldibenzoylmethane,4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4′diisopropylbenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane,4,4′-diisopropylbenzoylmethane,2-methyl-5-isopropyl-4′-methoxydibenzoymethane,2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane, and so on.Particularly preferred is 4-tert-butyl-4′-methoxydibenzoylmethane, alsoreferred to as Avobenzone. Avobenzone is commercial available fromGivaudan-Roure under the trademark Parsol 1789, and Merck & Co. underthe tradename Eusolex 9020.

Other types of UVA sunscreens include dicamphor sulfonic acidderivatives, such as ecamsule, a sunscreen sold under the trade nameMexoryl™, which is terephthalylidene dicamphor sulfonic acid, having theformula:

The composition may contain from about 0.001-20%, preferably 0.005-5%,more preferably about 0.005-3% by weight of the composition of UVAsunscreen. In the preferred embodiment of the invention the UVAsunscreen is Avobenzone, and it is present at not greater than about 3%by weight of the total composition.

UVB sunscreens may also be employed in the systems of the presentinvention. The term “UVB sunscreen” means a compound that blocks UVradiation in the wavelength range of from about 290 to 320 nm. A varietyof UVB chemical sunscreens exist includingalpha-cyano-beta,beta-diphenyl acrylic acid esters as set forth in U.S.Pat. No. 3,215,724, which is hereby incorporated by reference in itsentirety. One particular example of an alpha-cyano-beta,beta-diphenylacrylic acid ester is Octocrylene, which is 2-ethylhexyl2-cyano-3,3-diphenylacrylate. In certain cases the composition maycontain no more than about 110% by weight of the total composition ofoctocrylene. Suitable amounts range from about 0.001-10% by weight.Octocrylene may be purchased from BASF under the tradename Uvinul N-539.

Other suitable sunscreens include benzylidene camphor derivatives as setforth in U.S. Pat. No. 3,781,417, which is hereby incorporated byreference in its entirety. Such benzylidene camphor derivatives have thegeneral formula:

wherein R is p-tolyl or styryl, preferably styryl. Particularlypreferred is 4-methylbenzylidene camphor, which is a lipid soluble UVBsunscreen compound sold under the tradename Eusolex 6300 by Merck.

Also suitable are cinnamate derivatives having the general formula:

wherein R and R₁ are each independently a C₁₋₂₀ straight or branchedchain alkyl. Preferred is where R is methyl and R₁ is a branched chainC₁₋₁₀, preferably C₈ alkyl. The preferred compound is ethylhexylmethoxycinnamate, also referred to as Octoxinate or octylmethoxycinnamate. The compound may be purchased from GivaudanCorporation under the tradename Parsol MCX, or BASF under the tradenameUvinul MC 80. Also suitable are mono-, di-, and triethanolaminederivatives of such methoxy cinnamates including diethanolaminemethoxycinnamate. Cinoxate, the aromatic ether derivative of the abovecompound is also acceptable. If present, the Cinoxate should be found atno more than about 3% by weight of the total composition.

Also suitable as UVB screening agents are various benzophenonederivatives having the general formula:

wherein R through R₉ are each independently H, OH, NaO₃S, SO₃H, SO₃Na,Cl, R″, OR″ where R″ is C₁₋₂₀ straight or branched chain alkyl Examplesof such compounds include Benzophenone 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, and 12. Particularly preferred is where the benzophenone derivativeis Benzophenone 3 (also referred to as Oxybenzone), Benzophenone 4 (alsoreferred to as Sulisobenzone), Benzophenone 5 (Sulisobenzone Sodium),and the like. Most preferred is Benzophenone 3.

Also suitable are certain menthyl salicylate derivatives having thegeneral formula:

wherein R₁, R₂, R₃, and R₄ are each independently H, OH, NH₂, or C₁₋₂₀straight or branched chain alkyl. Particularly preferred is where R₁,R₂, and R₃ are methyl and R₄ is hydroxyl or NH₂, the compound having thename homomenthyl salicylate (also known as Homosalate) or menthylanthranilate. Homosalate is available commercially from Merck under thetradename Eusolex HMS and menthyl anthranilate is commercially availablefrom Haarmann & Reimer under the tradename Heliopan. If present, theHomosalate should be found at no more than about 15% by weight of thetotal composition.

Various amino benzoic acid derivatives are suitable UVB absorbersincluding those having the general formula:

wherein R₁, R₂, and R₃ are each independently H, C₁₋₂₀ straight orbranched chain alkyl which may be substituted with one or more hydroxygroups. Particularly preferred is wherein R₁ is H or C₁₋₈ straight orbranched alkyl, and R₂ and R₃ are H, or C₁₋₈ straight or branched chainalkyl. Particularly preferred are PABA, ethyl hexyl dimethyl PABA(Padimate 0), ethyldihydroxypropyl PABA, and the like. If presentPadimate 0 should be found at no more than about 8% by weight of thetotal composition.

Salicylate derivatives are also acceptable UVB absorbers. Such compoundshave the general formula:

wherein R is a straight or branched chain alkyl, including derivativesof the above compound formed from mono-, di-, or triethanolamines.Particular preferred are octyl salicylate, TEA-salicylate,DEA-salicylate, and mixtures thereof. Generally, the amount of the UVBchemical sunscreen present may range from about 0.001-45%, preferably0.005-40%, more preferably about 0.01-35% by weight of the totalcomposition.

A particularly preferred sunscreen agent is includingbisiminomethylguaiacol manganese chloride, in view of its cationiccharge.

If desired, the compositions of the invention may be formulated to havea certain SPF (sun protective factor) values ranging from about 1-50,preferably about 2-45, most preferably about 5-30. Calculation of SPFvalues is well known in the art.

The compositions of the invention may contain particulate materials inaddition to the optically reflective materials, including otherpigments, inert particulates, or mixtures thereof. Suggested ranges forall particulate materials is from about 0.01-75%, preferably about0.5-70%, more preferably about 0.1-65% by weight of the totalcomposition. In the case where the composition may comprise mixtures ofpigments and powders, suitable ranges include about 0.01-75% pigment and0.1-75% powder, such weights by weight of the total composition.

The particulate matter may be colored or non-colored (for example,white) non-pigmented powders. Suitable non-pigmented powders includebismuth oxychloride, titanated mica, fumed silica, spherical silica,polymethylmethacrylate, micronized teflon, boron nitride, acrylatecopolymers, aluminum silicate, aluminum starch octenylsuccinate,bentonite, calcium silicate, calcium aluminum borosilicate, cellulose,chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch,hectorite, hydrated silica, kaolin, magnesium aluminum silicate,magnesium trisilicate, maltodextrin, montmorillonite, microcrystallinecellulose, rice starch, silica, talc, mica, titanium dioxide, zinclaurate, zinc myristate, zinc rosinate, alumina, attapulgite, calciumcarbonate, calcium silicate, dextran, kaolin, nylon, silica silylate,silk powder, sericite, soy flour, tin oxide, titanium hydroxide,trimagnesium phosphate, walnut shell powder, or mixtures thereof. Theabove mentioned powders may be surface treated with lecithin, aminoacids, mineral oil, silicone, or various other agents either alone or incombination, which coat the powder surface and render the particles morelipophilic in nature.

The particulate materials may comprise various organic and/or inorganicpigments. The organic pigments are generally various aromatic typesincluding azo, indigoid, triphenylmethane, anthroquinone, and xanthinedyes which are designated as D&C and FD&C blues, browns, greens,oranges, reds, yellows, etc. Organic pigments generally consist ofinsoluble metallic salts of certified color additives, referred to asthe Lakes. Inorganic pigments include iron oxides, ultramarines,chromium, chromium hydroxide colors, and mixtures thereof. Iron oxidesof red, blue, yellow, brown, black, and mixtures thereof are suitable.Some embodiments contain melanin.

The composition may contain 0.001-8%, preferably 0.01-6%, morepreferably 0.05-5% by weight of the total composition of preservatives.A variety of preservatives are suitable, including benzoic acid, benzylalcohol, benzylhemiformal, benzylparaben, 5-bromo-5-nitro-1,3-dioxane,2-bromo-2-nitropropane-1,3-diol, butyl paraben, phenoxyethanol, methylparaben, propyl paraben, diazolidinyl urea, calcium benzoate, calciumpropionate, caprylyl glycol, hexylene glycol, biguanide derivatives,phenoxyethanol, captan, chlorhexidine diacetate, chlorhexidinedigluconate, chlorhexidine dihydrochloride, chloroacetamide,chlorobutanol, p-chloro-m-cresol, chlorophene, chlorothymol,chloroxylenol, m-cresol, o-cresol, DEDM Hydantoin, DEDM Hydantoindilaurate, dehydroacetic acid, diazolidinyl urea, dibromopropamidinediisethionate, DMDM Hydantoin, and the like. In certain preferredembodiments, the composition contains ethylhexyl glycerin orphenoxyethanol/chlorphenesin/glycerin/sorbic acid. In one preferredembodiment the composition is free of parabens.

The compositions of the invention may contain vitamins and/or coenzymes,as well as antioxidants. If so, 0.001-10%, preferably 0.01-8%, morepreferably 0.05-5% by weight of the total composition is suggested.Suitable vitamins include ascorbic acid and derivatives thereof such asascorbyl palmitate, tetrahexydecyl ascorbate, and so on; the B vitaminssuch as thiamine, riboflavin, pyridoxin, and so on, as well as coenzymessuch as thiamine pyrophoshate, flavin adenin dinucleotide, folic acid,pyridoxal phosphate, tetrahydrofolic acid, and so on. Also Vitamin A andderivatives thereof are suitable. Examples are retinyl palmitate,retinol. retinoic acid, as well as Vitamin A in the form of betacarotene. Also suitable is Vitamin E and derivatives thereof such asVitamin E acetate, nicotinate, or other esters thereof. In addition,Vitamins D and K are suitable.

Suitable antioxidants are ingredients which assist in preventing orretarding spoilage. Examples of antioxidants suitable for use in thecompositions of the invention are potassium sulfite, sodium bisulfite,sodium erythrobate, sodium metabisulfite, sodium sulfite, propylgallate, cysteine hydrochloride, butylated hydroxytoluene, butylatedhydroxyanisole, and so on. In one preferred embodiment, the compositioncontains pentaerythrityl tetra-di butyl hydroxyhydrocinnamate.

Embodiments herein further comprises treating skin for improvement byapplying to the skin the compositions of the invention. The systems maybe applied in the forms mentioned herein, as part of skin care regimens.For example, the system may be applied to the skin alone, orincorporated into a day cream. The systems may be applied aftercleansing the skin. The systems may be applied to the skin under or overskin care products, such as foundations or other color cosmetics orincorporated into such skin care products.

Dry, treated particulates described herein may be applied to clean, dryeyelashes after application of a coating of conventional mascara, orbetween applications of conventional mascara. Formulations according tothe present invention may take a variety of forms. The formulation maybe a mascara composition which is similar to a conventional mascara butwhich contains fibers treated according to embodiments herein; that is,fibers provided with a cationic coating, and, optionally, with a furthercoating containing film former and, with or without one or moreintermediate coatings between the initial cationic coating and the filmformer. One or more coats of the mascara containing fibers treatedaccording to the invention may be applied to the eyelashes to increasevolume and length of the lashes, depending on the user's needs. Theformulation also may take the form of a pigmented or unpigmented waxy-or gel-based composition containing the cationically-coated fibers in ahydrophilic carrier, such as water and alcohol. The latter formulationmay be applied to clean, dry eyelashes to provide enhanced volume andlength, optionally followed by the application of a conventionalmascara. Or, the waxy- or gel-based formula may be applied between coatsof conventional mascara. Formulations according to the present inventionwill not only enhance the volume and length of eyelashes of the user,but, due to the presence of the charged fibers, will result in wearwhich is superior to that achievable with fiber-containing conventionalproducts. It will be apparent to those of skill in the art that theformulations of the invention also may be used as a brow or hair filler.

The following examples further illustrate various specific embodimentsdescribed herein, without limiting the broad scope thereof.

EXAMPLES Example 1—Preparation of Treated Fibers Procedure:

1. 150 gms. of Splash Fiber II 7T 1 mm fibers (available from KoboProducts, Inc.) were introduced into the fluid bed of a microfluidizer(Glatt Air Techniques, model no. GPCG-1).2. Fibers were fluidized at 25% flap with the temperature set to 60° C.3. 150 gms. of a cationically charged solution containing 15 wt. %polyquaternium-6, 70 wt. % water and 15 wt. % denatured alcohol was topsprayed from the lower port of the fluidizer at 2.5 bar atomizing airpressure & 30 rpm pump speed over a period of about 19 minutes. Tominimize clumping of fibers, spraying was paused twice to allow thefibers to dry and start flowing again.4. Fibers were allowed to dry for 35 min with 60° C. inlet air.Levelling off of the product temperature for 10 minutes, followed byincreasing temperature, signalled that the moisture had been removed.5. 60 gms. of a film-former solution containing hydrophobic silicones asfollows: 52.19 wt. % methyl trimethicone, 35.4 wt. % trimethylsilicateand 12.41 wt. % dimethicone was top sprayed, from the lower port of theat 2.5 bar atomizing air pressure & 30 rpm pump speed over a period ofabout 7 minutes.6. Fibers were allowed to dry for 15 minutes with 60° C. inlet air.7. Confocal analysis confirmed that the fibers were completed coated.

Example 2—Attraction of Hair to Treated Fibers Procedure:

1. First and second hair swatches, weighing 1.36 gms. and 1.68 gms.,respectively were introduced into separate vessels containing eithercontrol fibers ((nylon-6 (and) black iron oxide (and) silica, availableas SPLASH FIBER II 7T-2MM, from Kobo Products, Inc.) or coated fibersprepared as in Example 1.2. After about 2 minutes, each of the hair swatches was removed from therespective vessels and re-weighed.

Result:

It was observed that the swatch introduced into the vessel containingthe control fibers still weighed 1.36 gms., while the hair swatchintroduced into the vessel containing the treated fibers weighed 1.70gms. indicating that the hair swatch attracted 0.02 gms of treatedfibers.

Example 3—Preparation of Treated Fibers Procedure:

1. 300 gms. of Silk Cotton PW fibers (available from Kobo Products,Inc.) were introduced into the fluid bed fo a microfluidizer.2. Fibers were fluidized at 25% flap with the temperature set to 20° C.3. 300 g of a cationically charged solution containing 15 wt. % polyquaternium-6, 70 wt. % water and 15 wt. % denatured alcohol was topsprayed from the lower port of the fluidizer at 2.5 bar atomizing airpressure & 30 rpm pump speed over a continuous period of about 40minutes.4. Fibers were permitted to dry for 50 minutes with 60° C. inlet air.Levelling off of the product temperature for 10 minutes, followed byincreasing temperature, signalled that the moisture had been removed.5. 300 gms. of a dispersion of hydrophilic film-former, polyurethane-35in water (41 wt. % polyurethane in water, available as Baycusan C 1004from Covestro) was top sprayed, from the lower port of the fluidizer, at2.5 bar atomizing air pressure & 30 rpm pump speed over a period of 38minutes.6. Fibers were dried for 50 minutes with 60° C. inlet air.7. Confocal analysis confirmed that the fibers were completed coated.

Example 4—Dispersibility of Fibers in Water Procedure:

1. 5 gms of each of the treated Silk Cotton PW fibers of Example 3, SilkCotton PW fibers coated only with the cationically charged material usedin Example 3, and untreated control Silk Cotton PW fibers, weredispersed in separate vessels, each containing 50 ml water.2. After 10 minutes, it was observed that the twice-coated Silk CottonPW fibers presented as two phases; the hydrophobic fibers not beingwater-dispersible, floated to the top of the water. The fibers receivingonly the cationically charged coating were partially dispersible, somefibers settling to the bottom of the vessel. The control fibers,absorbing water, settled to the bottom of the vessel.

Example 5—Preparation of Treated Fibers Procedure:

1. 200 gms. of Splash Fiber II 7T 1 mm were introduced into the fluidbed of a fluidizer.2. Fibers were fluidized at 25% flap with the temperature set to 20° C.3. 100 gms. of a cationically charged solution containing 15 wt. % polyquaternium-6, 70 wt. % water and 15 wt. % denatured alcohol was topsprayed from the lower port of the fluidizer at 2.5 bar atomizing airpressure & 30 rpm pump speed until fibers were observed to clump andfluidization was lost.4. Fibers were dried for 15 minutes with inlet air at 60° C. to driveoff sufficient moisture until fluidization resumed. Inlet air remainedon for the remainder of the process.5. An additional 100 gms. of the cationically charged solutioncontaining 15 wt. % poly quaternium-6, 70 wt. % water and 15 wt. %denatured alcohol was top sprayed from the lower port of the fluidizerat 2.5 bar atomizing air pressure & 30 rpm pump speed until fibers wereobserved to clump and fluization was lost.6. The fibers then were dried at 60° C. with inlet air for 50 minutes.7. 200 gms. of of a dispersion of hydrophilic film-former,polyurethane-35, in water (available from Covestro as Baycusan C1004—was top sprayed, from the lower port of the fluidizer, at 2.5 baratomizing air pressure & 30 rpm pump speed over a period of 20 minuteswith no significant clumping observed.8. Fibers were dried at 60° C. for 50 minutes.9. Confocal analysis confirmed that the fibers were completed coated.

Example 6—Preparation of Treated Fibers Procedure:

1. 100 gms of NFBL-10D-1R ((nylon-6 (and) iron oxides (and)triethoxycapryl silane (and) silica, available from Kobo Products,Inc.)) was introduced into the bed of a fluidizer.2. Fibers were fluidized at 25% flap with the temperature set to 20° C.3. 100 gms. of a cationically charged solution containing 15 wt. % polyquaternium-6, 70 wt. % water and 15 wt. % denatured alcohol was topsprayed from the lower port of the fluidizer at 2.5 bar atomizing airpressure & 10 rpm pump speed until fibers were observed to clump andfluidization was lost.4. Fibers were dried for 15 minutes with inlet air at 60° C. to driveoff sufficient moisture until fluidization resumed. Inlet air remainedon for the remainder of the process.5. 100 gms. of a film-former solution containing a mixture of 59.46 wt.% trisiloxane, 20.27 wt. % dimethicone and 20.27 wt. %trimethylsiloxysilicate was top sprayed, from the lower port of thefluidizer, at 2.5 bar atomizing air pressure & 5 rpm pump speed over aperiod of 20 minutes with no significant clumping observed.6. Fibers were dried at 60° C. for 50 minutes.7. Confocal analysis confirmed that the fibers were completed coated.The zeta potential (measured by Brookhaven Instruments, model NanoBrookOmni 28001, spectrophotometer) of the treated fibers was determined tobe 143 mV.

Example 7—Preparation of Treated Fibers Procedure:

Example 6 was repeated except that the film-former solution contained amixture of 59.1 wt. % trisiloxane, 18.43 wt. % dimethicone, 21.87 wt. %trimethylsiloxysilicate and 0.6 wt. % polyglyceryl-3 siloxanedimethicone.

Example 8—Preparation of Treated Fibers Procedure:

Example 6 was repeated except that the fibers were sprayed with 25 wt. %of a cationically charged solution contained 15 wt. % polyquaternium-6,70 wt. % water and 15 wt. % denatured alcohol. The cationically chargedfibers were sprayed with 5 wt. % of a film former solution contained59.46 wt. % trisiloxane, 20.27 wt. % dimethicone, and 20.27 wt. %trimethylsiloxysilicate. The zeta potential of the treated fibers wasdetermined to be 79 mV.

Example 9—Preparation of Treated Fibers Procedure:

Example 8 was repeated except that the cationically charged fibers weresprayed with 7.5 wt. % of a film former solution containing 59.46 wt. %trisiloxane, 20.27 wt. % dimethicone and 20.27 wt. %trimethylsiloxysilicate. The zeta portential of the treated fibers wasdetermined to be 59 mV.

Example 10—Preparation of Treated Fibers Procedure:

Example 8 was repeated except that the cationicaly charged fibers weresprayed with 3.75 wt. % of a film former solution containing 59.46 wt. %trisiloxane, 20.27 wt. % dimethicone and 20.27 wt. %trimethylsiloxysilicate.

Example 11—Preparation of Treated Fibers Procedure:

The process of Example 6 was repeated except that an intermediatecoating of 0.1 weight percent aqueous solution of grapeseed extract wassprayed on the cationically coated fibers prior to coating with the filmformer solution.

Example 12—Preparation of Treated Fibers Procedure:

The process of Example 6 was repeated except that the initial cationiccoating contained 0.2 gms powdered iron (FeO) in a watery gel containing60.7 wt. % water, 0.1 wt. % hydroxyethylcellulose and 39 wt. %.

Example 13—Gel-based Treated Fiber-Containing Formulation

Weight Sequence Ingredients Percent 1 water 59.70 1 ammoniumacryloyldimethyltaurate/beheneth-25 1.50 methacrylate crosspolymer 1sodium dehydroacetate 0.50 1 disodium EDTA 0.05 1 sodium benzoate 0.05 2black iron oxide/calcium alginate/calcium chloride/ 9.00 sodium chloride3 glycerine 4.00 4 polyurethane-35/water 20.00 5 phenoxyethanol 0.80 5*treated fibers 4.00 5 silica 0.40 TOTAL 100.00 *prepared in Example 5

Procedure:

1. Sequence 1 ingredients were mixed in main beaker with agitation at35° C. for one hour.2. Sequence 2 ingredient was added to the main beaker and the batchmixed with a homogenizer at room temperature for 20 minutes.3. Sequence 3 and sequence 4 ingredients were added to the main beakerand the batch mixed with the homogenizer for 10 minutes.4. Sequence 5 ingredients were added to the main beaker and the batchmixed with the homogenizer for 10 minutes.

Example 14—Mascara Formulation Containing Treated Fibers

Weight Sequence Ingredients Percent 1 water 17.8799 1hydroxyethylcellulose 0.4000 2 water 1.0000 2 aminomethyl propanediol0.2500 3 water 10.0000 3 hydroxyethylcellulose 0.1000 4 isostearic acid0.2500 5 iron oxides 10.0000 5 *treated fibers 2.0000 6 water 2.0000 7polyvinylpyrrolidone 0.8000 7 calcium aluminum borosilicate 0.1000 7sodium dehydroacetate 0.2000 7 silica 4.9000 7 disodium EDTA 0.1000 8pantethine 0.0300 8 panthenol 0.0300 8 melanin 0.0100 9 water 1.0000 9dimethicone 0.1000 10 isostearic acid 0.3500 10 pentaerythrityl tetra-dibutyl 0.0500 hydroxyhydrocinnamate 10 stearic acid 6.6000 10 carnauba7.3500 10 glyceryl stearate 5.7000 10 polyisobutene 5.7000 10 lauroyllysine 0.0100 10 vinylpyrrolidone/eicosene copolymer 1.5000 11 water1.2000 12 water 2.7000 12 aminomethyl propanediol 1.3500 13 water 3.000013 acacia Senegal gum 0.2500 14 dimethicone PEG-8 polyacrylate 3.0000 15water/acrylates copolymer 7.0000 16 water 1.1940 16 sodium hyaluronate0.0060 17 water/hydrolyzed wheat protein 0.0001 17phenoxyethanol/chlorphenesin/glycerin/sorbic 1.3000 acid 18ethylhexylglycerin 0.5000 TOTAL 100.0000 *prepared in Example 10

Procedure:

1. Sequence 1 ingredients were mixed in main beaker with mixing at 45°C. for 20 minutes.2. Sequence 2 ingredients were added to a separate beaker and mixed withpropeller at room temperature until dissolved.3. Sequence 3 ingredients were added to a separate beaker and mixed withprop at 45° C. for 20 minutes.4. Sequence 3, 4 and 5 ingredients were added to a separate beaker andhomogenized for 20 minutes at room temperature.5. The ingredients of steps 2 and 4 were added to the main beaker withmixing.6. Sequence 6 and 7 ingredients were mixed in a separate beaker untildissolved at room temperature, and were then added to the main beaker.7. Sequence 8 ingredients were added to the main beaker, and the mainbeaker heated to 85° C. while mixing for 5 minutes.8. Sequence 9 ingredients were added to the main beaker whilemaintaining beaker temperature at 85° C. with mixing for 5 minutes.9. Sequence 10 ingredients were added to a separate beaker while heatingto 90° C. with propeller mixing until uniform.10. The batch of step 9 was pour slowly into the main beaker to avoidair entrapment while homogeneous mixing and maintaining temperature ofmain beaker between 85-90° C.11. Sequence 11 ingredient was used to rinse beaker containing residualSequence 10 ingredients.12. Sequence 12 ingredients were mixed at room temperature untildissolved and clear and then were added to the main beaker.13. Sequence 13 ingredients were mixed until uniform and then added tothe main beaker.14. Sequence 14 ingredient was added to the main beaker with mixing.15. Sequence 15 ingredient was added to the main beaker with mixing.16. Sequence 16 ingredients were mixed until uniform and then themixture was added to the main beaker.17. Sequence 17 ingredients were added individually to the main beaker,while mixing for 5 minutes.18. Sequence 18 ingredient was added to the main beaker with continuousmixing for 10 minutes.

Example 15—Evaluation of Treated Fibers by Confocal MicroscopyProcedure: A.

1. 0.02 wt. % fluorescein sodium salt was added to 99.98 wt. % of acationic coating solution comprising 15 wt. % polyquaternium-6, 70 wt. %water and 15 wt. % alcohol. The solution was used to spray coat 100 gmsNFBL-10D 1R fibers in a microfluidizer according to the proceduresdescribed hereinabove.

2. To evaluate the uniformity of the coating on the fibers, 0.02 gmsamples of the coated fibers were examined under a confocal microscopewith transmission light (about 300 nm) and laser light (about 488 nm),respectively. Under laser light, it was observed that the entireperipheral surfaces of every fiber fluoresced indicating that each fiberwas fully encapsulated with the cationic coating. No fluorescence wasobserved under transmission light.

B.

1. Step A1 was repeated.

2. The cationically coated fibers were then subjected to a spray coatingcontaining 3 wt. % of a silicone blend (52.19 wt. % methyltrimethicone,35.4 wt. % trimethylsiloxysilicate and 12.41 wt. % dimethicone).

3. To evaluate the uniformity of the cationic coating on the fibers, andto ascertain whether the silicone blend would permit or blockillumination of the fluorescein, 0.02 gm samples of the coated fiberswere examined under a confocal microscope with transmission light andwith laser light, respectively. It was observed that the entireperipheral surface of each fiber fluoresced under the laser lightindicating that the cationic coating remained uniform.

C.

1. Step A1 was repeated.

2. The cationically coated fibers were washed 20 times, for 30 minuteseach time, in water at 3000 rpm in a centrifuge and then dried in anincubator overnight at 50° C.

3. To evaluate the uniformity of the cationic coating on the fibers,0.02 gm samples of the cationically coated fibers were examined under aconfocal microscope with transmission light and with laser light,respectively. Under laser light, it was confirmed that all of thecationic coating had been removed from the fibers, as observed by thelack of fluorescence.

D.

1. Steps C 1 and 2 were repeated except that the cationically coatedfibers were washed only once, and dried.

2. The washed fibers were then spray coated with a 3 wt. % of a siliconeblend containing 52.19 wt. % methyltrimethicone, 35.4 wt. %trimethylsiloxysilicate and 12.41 wt. % dimethicone.

3. The fibers of step 2 were then washed 20 times, and then dried, asdescribed above.

4. To evaluate the uniformity of the cationic coating on the fibers,0.02 gm samples of the cationically coated fibers were examined under aconfocal microscope with transmission light and with laser light,respectively. The observation of the illumination of the entireperiphery of each fiber under laser light confirmed that each fiberremained fully coated with the cationic material. The silicone coatingnot only sealed the cationic coating to the fibers but also rendered thefibers water-resistant.

Example 16—Virgin (Non-Charged) Fibers and Film-Former-CoatedCationically Charged Fibers

1. 1-2 grams of virgin fibers (nylon-6: NFCB-10D-1R 1 mm—nylon fiber/FDAcertified carbon black/10 denier/1 mm/round, available from Daito KaseiKogyo Co. Ltd.) were loosely packed, using a spatula, into a tubeequipped with a wiper, and the tube was secured with a cap fitted with abrush. 1-2 grams of cationically-charged fibers (nylon-6: NFCB-10D-1R 1mm nylon fiber/FDA certified carbon black/10 denier/1 mm/round, obtainedfrom Daito Kasei Kogyo Co. Ltd., subsequently encapsulated withpolyquaternium-6, and then further treated with a hydrophilicfilm-former coating of dimethicone andtrimethylsiloxysilicate/polyglyceryl-3 siloxane dimethicone intrisiloxane were loosely packed, using a spatula, into a separate tubeequipped with a wiper, and the tube was secured with a cap fitted with abrush.

2. The respective caps were then removed from each of the tubes, thebrush in each tube, loaded with fibers, being withdrawn through thewiper, over separate blank sheets of white paper.

3. FIG. 1 shows fibers scattered over the initially blank white paper.Virgin fibers carry no charge of their own; however, as the brush loadedwith fibers was withdrawn from the tube, through the wiper, the frictionproduced by the brush moving through the wiper caused the brush to bestatically (i.e., relatively negatively) charged. The previouslyuncharged virgin fibers captured in the bristles of the brush alsobecame negatively charged by attracting negative charges from theatmosphere. The statically charged fibers repelled one another as wellas the brush. It was further observed that the brush could not be fullyinserted back into the tube after being withdrawn. Prior to the brushbeing withdrawn, the fibers were loosely entangled about one anotheraround the brush in the tube. Inserting the negatively charged brushback into the tube through the wiper caused the entangled fibers to becompacted in the bottom of the tube so that the brush could not bereloaded with fibers.

4. FIG. 2 depicts a blank sheet of paper, since the film-former coated,cationically charged fibers according to the invention, did not scatterfrom the brush onto the paper as the brush was withdrawn from the tube,but remained entrapped in the bristles of the brush. Although thefriction caused by the brush moving through the wiper caused the brushto be statically (i.e., relatively negative) charged, and although thefilm-former coated, cationically-charged fibers according to theinvention also picked up negative charges from the atmosphere, thepositive and negative charges on the fibers briefly canceled each otherout. As a result, the fibers did not repel one another. As the staticcharge on the fibers dissipated, the positively charged fibers adheredto the negatively charged brush. The brush was easily re-inserted intothe tube because the coated, cationically charged fibers in the tube didnot agglomerate or compact.

Example 17—Virgin (Uncharged) Fibers and Coated, Cationically ChargedFibers Applied to Lashes

1. Separate tubes of loosely packed virgin fibers and film-formercoated, cationically-charged fibers were provided as indicated inExample 16.

2. A panelist applied a first coat of a commercial (non-waterproof)mascara to the lashes of both eyes.

3. The panelist immediately thereafter applied the virgin fibers to themascara-coated lashes of the right eye, using the brush applicator,while the mascara was still tacky. The panelist then applied the filmformer-coated, cationically-charged fibers, using the brush applicator,onto the lashes of the left eye while the mascara was still tacky. Thepanelist noted that the virgin fibers were difficult to apply and beganto fall to the cheek during application. As shown in FIG. 3, while somefibers adhered to the lashes, fibers also flew about and about 90 fiberswere counted on the skin of the right cheek and the right side of thenose. On the other hand, the coated, cationically-charged fibers weresmoothly and easily applied, and adhered well to the lashes. Asdiscussed above in Example 16, while the virgin fibers carried staticcharges which caused them to repel one another and neither adhere wellto the brush or to the lashes, the positively charged fibers of theinvention adhered to the brush carrying the static (i.e., negative)charges and to the negatively charges lashes.

4. Any fallen fibers were then wiped clean from both undereye areasincluding the cheek and the nose.

5. One hour after the initial applications of fibers to themascara-coated lashes, about 30 virgin fibers were observed on the skinof the cheek under the right eye, as shown in FIG. 4. Additionally, eyeirritation was reported. In contrast, the film-former coated,cationically-charged fibers of the invention remained adhered to thelashes. Only two fibers were observed to have fallen on the undereyearea of the left eye, as shown in FIG. 5.

Increasing the Charge of the Treated Fibers

As noted previously, cationically charged particulates adhere tonegatively charged keratinous materials, such as lashes or hair. Thecationic charge of the treated particulates described herein can furtherbe increased when used with certain applicators and containers. It isimportant to have an optimal cationic charge on the fibers. If thecharge on the fibers is too high (i.e., over 65 mV), the fibers wouldrepel each other, which could result in insufficient amount deposited onthe lashes. If the charge on the fibers is too low (i.e., below 3 mV),the attraction between the cationic fibers and the negatively chargedlashes would be inadequate for the fibers to adhere to the lashes, whichcould result in insufficient volume as fewer fibers would adhere to thelashes.

The amount of treated fibers deposited on lashes (observed visually) asa function of charge is shown in FIG. 6. As shown in FIG. 6, the amountof fibers deposited on the lashes increases as a function of charge, butonly up until approximately 50 my to 65 mV, and the amount of fibersdeposited decreases thereafter.

Advantageously, embodiments herein provide for optimal adherencebenefits by treating particulates as described herein to result in acationic charge in the range of 3 mV to 65 mV, thereby providing formaximized deposit of treated particulates on lashes through attractionbetween the cationically charged particulates and the negatively chargedlashes.

In various embodiments, the treated fibers described in the examplesabove can be placed into a container (e.g. a mascara bottle) and appliedwith an applicator (e.g., a mascara wand). When the mascara wand, whichhas picked up some of the treated fibers, makes contact with the mascarawiper in the bottle, a static charge is generated by the friction. Thestatic charge is then transferred to the fibers, thereby increasing thecationic charge of the treated fibers on the mascara wand. The mascarawand or applicator may be made of a thermoplastic (or synthetic)polymer, for example, but not limited to polypropylene,polyoxymethylene, and combinations thereof. The mascara bottle and/orwiper may be made of polyethylene.

The following examples illustrate the increase in cationic charge to thetreated fibers using a mascara wand and wiper. While a mascara wand andwiper were used in the example below, other containers and applicatorsmay be used. The control used is untreated fiber. The fibers weretreated as described in Example 18 below.

Example 18—Preparation of Treated Fibers Procedure:

1. 100 gms of NFBL-10D-1R fibers was introduced into the bed of afluidizer.2. Fibers were fluidized at 25% flap with the temperature set to 20° C.3. 100 gms. of a cationically charged solution containing 15 wt. % polyquaternium-6, 78 wt. % water and 7 wt. % denatured alcohol was topsprayed from the lower port of the fluidizer at 2.5 bar atomizing airpressure & 10 rpm pump speed until fibers were observed to clump andfluidization was lost.4. Fibers were dried for 15 minutes with inlet air at 60° C. to driveoff sufficient moisture until fluidization resumed. Inlet air remainedon for the remainder of the process.5. 100 gms. of a film-former solution containing a mixture of 90.3 wt. %dimethicone, 9.44 wt. % trimethylsiloxysilicate, and 0.26 wt. %polyglyceryl-3 siloxane dimethicone was top sprayed, from the lower portof the fluidizer, at 2.5 bar atomizing air pressure & 5 rpm pump speedover a period of 20 minutes with no significant clumping observed.6. Fibers were dried at 60° C. for 50 minutes.

The fibers were treated according to Example 18 above and placed into apolyethylene container, a polypropylene wand was then inserted into thecontainer of treated fibers. The wand, which picked up some of thetreated fibers, was then pulled out of the container and rubbed or wipedagainst the wiper portion of the container at least once. The tablesbelow show results of five, fifteen, and forty frictions (e.g., rubbingor contacting the mascara wand against the mascara wiper), but fewer ormore frictions may be performed.

The control (untreated fibers) contains approximately 1.5 g of neatfibers and the treated fibers contains approximately 2.4 g of coatedfibers. Both samples were placed into the same component type for easeof comparison. Approximately 0.3 g of fibers was taken for the Zetapotential evaluation each time. Each sample was ran three times toobtain the average. A Zeta Potential & Particle Size Analyzer fromBrookhaven Instrument Model#: Nano Brook Omni was used in the analysis.

TABLE 1 Untreated fibers, initial charge Sample Zeta Potential ID (mV)Sample 1 −4.26 Sample 2 −9.81 Sample 3 −5.18 Mean: −6.42 Standard Error:1.72 Standard Deviation: 2.97

TABLE 2 Control after 5 frictions Sample Zeta Potential ID (mV) Sample 1−6.25 Sample 2 3.64 Sample 3 −3.24 Mean: −1.95 Standard Error: 2.93Standard Deviation: 5.07

TABLE 3 Untreated fibers, charge after 15 frictions Sample ZetaPotential ID (mV) Sample 1 3.48 Sample 2 5.24 Sample 3 0.56 Mean: 3.09Standard Error: 1.37 Standard Deviation: 2.37

TABLE 4 Control after 40 frictions Sample Zeta Potential ID (mV) Sample1 −2.65 Sample 2 −4.73 Sample 3 3.99 Mean: −1.13 Standard Error: 2.63Standard Deviation: 4.55

TABLE 5 Fibers treated according to Example 18, initial charge SampleZeta Potential ID (mV) Sample 1 8.10 Sample 2 2.07 Sample 3 8.97 Mean:6.38 Standard Error: 2.17 Standard Deviation: 3.76

TABLE 6 Fibers treated according to Example 18, charge after 5 frictionsSample Zeta Potential ID (mV) Sample 1 18.75 Sample 2 29.15 Sample 324.23 Mean: 24.04 Standard Error: 3.01 Standard Deviation: 5.21

TABLE 7 Fibers treated according to Example 18, charge after 15frictions Sample Zeta Potential ID (mV) Sample 1 28.78 Sample 2 27.85Sample 3 28.66 Mean: 28.43 Standard Error: 0.29 Standard Deviation: 0.50

TABLE 8 Fibers treated according to Example 18, charge after 40frictions Sample Zeta Potential ID (mV) Sample 1 24.59 Sample 2 33.69Sample 3 27.75 Mean: 28.68 Standard Error: 2.67 Standard Deviation: 4.62

As shown in the tables above, the average initial static charge of theneat or untreated fibers is −6.42 mV and the average initial staticcharge of the treated fibers is 6.38 mV. After five frictions (e.g.,five times of rubbing the rod against the wiper), the control showed anaverage increase in the static charge to −1.95 mV and the average staticcharge of the treated fibers increased to 24.04 mV. After fifteenfrictions, the average static charge of the control and the treatedfibers increased to 3.09 mV and 28.43 mV. After forty frictions, theaverage static charge for the control decreased to −1.13 mV, whereas thetreated fibers show an increase in the average static charge to 28.68mV.

As evidenced by the results, the untreated fibers possess a negativecharge (anionic charge) initially. After friction, the static chargestarts to build up after five frictions and fifteen frictions. However,after forty frictions, the charge of the untreated fibers drops backdown to negative and the untreated fibers were unable to retain acationic charge. In contrast, the fibers treated according to themethods described herein possess a positive (cationic) charge initially,and the positive charge builds up and increases with successivefrictions. Accordingly, the results in Tables 1-8 above show thatparticulates treated according to methods described herein retain morecationic charge than untreated particulates.

Although the invention has been variously disclosed herein withreference to illustrative embodiments and features, it will beappreciated that the embodiments and features described hereinabove arenot intended to limit the scope of the invention, and that othervariations, modifications and other embodiments will suggest themselvesto those of ordinary skill in the art. The invention therefore is to bebroadly construed, consistent with the claims hereafter set forth.

What is claimed is:
 1. A method of increasing cationic charge ofparticulates, comprising: coating a rod with cationically chargedparticulates; contacting the rod with a surface at least once togenerate a static charge; and transferring the static charge to thecationically charged particulates on contact with the surface.
 2. Themethod of claim 1, wherein the rod comprises a thermoplastic polymer. 3.The method of claim 2, wherein the thermoplastic polymer is selectedfrom the group consisting of polypropylene, polyoxymethylene, andcombinations thereof.
 4. The method of claim 1, wherein the staticcharge generated is in the range of 3 mV to 65 mv.
 5. The method ofclaim 1, wherein contacting the rod with the cationically chargedparticulates comprises inserting the rod into a composition comprisingthe cationically charged particulates.
 6. The method of claim 5, whereinthe composition is in the form of a mascara, a brow filler or a hairfiller.
 7. The method of claim 5, wherein the composition is in the formof an aqueous-containing solution, a dispersion or an emulsion.
 8. Themethod of claim 1, wherein the rod is a mascara wand and the surface isa mascara wiper.
 9. The method of claim 8, wherein contacting the rodwith the surface comprises wiping the mascara wand against the mascarawiper to generate the static charge.
 10. The method of claim 8, whereinthe mascara wiper comprises polyethylene.
 11. The method of claim 1,wherein the cationically charged particulates comprise particulatesencapsulated in a first coating comprising a first material, and in asecond, outer coating comprising a second material, the first coatingcomprising a cationically-charged material in an amount sufficient toimpart a cationic charge in the range of from about 0.1 mV to about 400mV to the particulates, and the second coating comprising a film formermaterial in an amount sufficient to render the particulates hydrophobic,wherein a weight ratio of the cationically-charged material to theparticulates is in the range of from about 0.1:1 to about 5:1.
 12. Themethod of claim 11, wherein the second, outer coating comprises a filmformer material comprising a silicone, an acrylates polymer, anacrylates copolymer, a polyvinylpyrrolidone (PVP) derivative, apolyurethane, a polyvinyl amine, a polyvinyl acetate, sucrose acetateisobutyrate, or a combination of any two or more thereof.
 13. The methodof claim 11, wherein the cationically-charged material comprises anaturally-derived or a synthetic cationic polymer.
 14. The method ofclaim 13, wherein the synthetic cationic polymer comprisespolyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-10,polyquaternium-39, polyquaternium-44, polyquaternium-46,distearyldimonium chloride, cinnamidopropyltrimonium chloride,cetrimonium chloride, guar hydroxypropyltrimonium chloride, or acombination of any two or more thereof.
 15. The method of claim 13,wherein the naturally-derived cationic polymer comprises a cationicallycharge-modified derivative of one or more of guar gum, cellulose, aprotein, a polypeptide, chitosan, lanolin, or a starch.
 16. Thecomposition of claim 13, wherein the particulates are in the form ofsynthetic powder particulates, synthetic fibers, or a combinationthereof.